Porous shaped carbon products

ABSTRACT

Shaped porous carbon products and processes for preparing these products are provided. The shaped porous carbon products can be used, for example, as catalyst supports and adsorbents. Catalyst compositions including these shaped porous carbon products, processes of preparing the catalyst compositions, and various processes of using the shaped porous carbon products and catalyst compositions are also provided.

REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional application Ser.No. 62/247,721, filed Oct. 28, 2015, the entire disclosure of which isincorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to shaped porous carbon productsand processes for preparing these products. The shaped porous carbonproducts can be used, for example, as catalyst supports, chromatographicsupport material, filtration media and adsorbents. The present inventionalso relates to catalyst compositions including these shaped porouscarbon products, processes of preparing the catalyst compositions, andvarious processes of using the shaped porous carbon products and thecatalyst compositions.

BACKGROUND OF THE INVENTION

Carbon is a material that can be deployed as a catalyst support oradsorbent. The most commonly used carbon based supports for chemicalcatalysis are activated carbons exhibiting high specific surface areas(e.g., over 500 m²/g). Preparing activated carbon requires activating acarbonaceous material such as charcoal, wood, coconut shell orpetroleum-sourced carbon black either by a chemical activation, such ascontacting with an acid at high temperatures, or by steam activation.Both methods of activation produce high concentrations of micropores andconsequently higher surface areas. Depending upon the source of thecarbonaceous material, the resultant activated carbons may have a highresidual content of inorganic ash and sulfur, and possibly oxygen ornitrogen-containing functional groups at the surface. Activated carbonsare thought to possess an optimum support structure for catalyticapplications as they enable good dispersion of catalytically activecomponents and effective adsorption and reaction of chemical reagents atthe catalyst surface.

In recent years, there has been a growing interest in using biorenewablematerials as a feedstock to replace or supplement crude oil. See, forexample, Klass, Biomass for Renewable Energy, Fuels, and Chemicals,Academic Press, 1998. This publication and all other cited publicationsare incorporated herein by reference. One of the major challenges forconverting biorenewable resources such as carbohydrates (e.g., glucosederived from starch, cellulose or sucrose) to current commodity andspecialty chemicals is the selective removal of oxygen atoms from thecarbohydrate. Approaches are known for converting carbon-oxygen singlebonds to carbon-hydrogen bonds. See, for example, U.S. Pat. No.8,669,397, which describes a process for the conversion of glucose toadipic acid via the intermediate glucaric acid. One challenging aspectassociated with the catalytic conversions of highly functionalizedbiorenewably-derived molecules and intermediates is reaching the highlevels of catalytic activity, selectivity and stability necessary forcommercial applications. With respect to catalytic activity andselectivity, highly functionalized, biorenewably-derived molecules andintermediates derived from carbohydrates (e.g., glucose and glucaricacid) are non-volatile and must therefore be processed as solutions inthe liquid phase. When compared to gas phase catalytic processes, liquidphase catalytic processes are known to suffer from lower productivitiesbecause liquid to solid (and gas to liquid to solid) diffusion rates areslower than gas to solid diffusion rates.

Another challenging aspect associated with the catalytic conversion ofhighly functionalized biorenewably-derived molecules and intermediatesis the use of chemically aggressive reaction conditions. For example,U.S. Pat. No. 8,669,397 describes catalytic conversion steps performedat elevated temperatures in the presence of polar solvents such as waterand acetic acid. Polar solvents are typically required for thedissolution of non-volatile, highly-functionalized molecules such asglucose and glucaric acid, and elevated temperatures are required forproductive and affordable catalytic conversion steps for commoditychemical applications. Therefore, a significant challenge associatedwith the catalytic conversion of highly functionalizedbiorenewably-derived molecules and intermediates is catalyst stability.Long term catalyst stability is a necessity for commodity chemicalproduction, meaning that the catalyst must be stable, productive, andselective under reaction conditions for long periods.

The challenges associated with the development of industrial shapedcatalysts, especially in the conversion of biorenewably-derivedmolecules and intermediates, are a) high productivity and selectivityconsistent with an economically viable catalyst at industrial scale, b)mechanical and chemical stability of the shaped catalyst support and c)retention of the catalytically active components by the support and theavoidance of leaching of the catalytically active components into apolar solvent reaction medium. There remains a need for industriallyscalable, highly active, selective and stable catalyst supports andcatalyst compositions that can satisfy these challenges.

SUMMARY OF THE INVENTION

Briefly, in various aspects, the present invention is directed toprocesses for preparing shaped porous carbon products. In accordancewith various embodiments, processes for preparing a shaped porous carbonproduct comprise mixing a carbonaceous material and an organic binder toform a carbon-binder mixture, wherein the binder comprises: (i) asaccharide selected from the group consisting of a monosaccharide, adisaccharide, an oligosaccharide, a derivative thereof, and anycombination thereof and/or (ii) a water soluble polymer; forming thecarbon-binder mixture to produce a shaped carbon composite; and heatingthe shaped carbon composite in a heating zone to carbonize the binderthereby producing the shaped porous carbon product.

In accordance with other embodiments, processes for preparing a shapedporous carbon product comprise mixing water, a carbonaceous material,and an organic binder to form a carbon-binder mixture, wherein thebinder comprises: (i) a saccharide selected from the group consisting ofa monosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and/or (ii) a water solublepolymer; forming the carbon-binder mixture to produce a shaped carboncomposite; and heating the shaped carbon composite in a heating zone tocarbonize the binder thereby producing the shaped porous carbon product,wherein the heating zone comprises at least two heating stages that areeach maintained at an approximately constant temperature and thetemperature of each stage differs by at least about 50° C., at leastabout 100° C., at least about 150° C., at least about 200° C., at leastabout 250° C., at least about 300° C., at least about 350° C., or atleast about 400° C.

In accordance with further embodiments, processes for preparing a shapedporous carbon product comprise mixing water, a carbonaceous material,and an organic binder to form a carbon-binder mixture, wherein thebinder comprises: (i) a saccharide selected from the group consisting ofa monosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and/or (ii) a water solublepolymer; forming the carbon-binder mixture to produce a shaped carboncomposite; and heating the shaped carbon composite in a heating zone tocarbonize the binder thereby producing the shaped porous carbon product,wherein the heating zone comprises: (1) a first heating stage where theshaped carbon composite is heated at a first temperature; and (2) asecond heating stage where the shaped carbon composite is heated at asecond temperature and wherein the first and second temperature are eachapproximately constant and the second temperature is greater than thefirst temperature by at least about 50° C., at least about 100° C., atleast about 150° C., at least about 200° C., at least about 250° C., atleast about 300° C., at least about 350° C., or at least about 400° C.

Other embodiments are directed to processes for preparing a shapedporous carbon product that comprise mixing water, a carbonaceousmaterial, and an organic binder to form a carbonaceous material mixture,wherein the binder comprises: (i) a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof and/or (ii) a watersoluble polymer; forming the carbonaceous material mixture to produce ashaped carbon composite; and heating the shaped carbon composite in aheating zone to carbonize the binder thereby producing the shaped porouscarbon product, wherein the heating zone comprises a continuous rotarykiln.

Further embodiments are directed to processes for preparing a shapedporous carbon product that comprise mixing water, a carbonaceousmaterial, and an organic binder to form a carbon-binder mixture, whereinthe binder comprises: (i) a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof and/or (ii) a watersoluble polymer; forming the carbon-binder mixture to produce a shapedcarbon composite; drying the shaped carbon composite at a temperaturefrom about 90° C. to about 150° C., from about 100° C. to about 150° C.,or from about 100° C. to about 140° C., wherein the water content of theshaped carbon composite after drying is no greater than about 25 wt. %,no greater than about 20 wt. %, no greater than about 15 wt. %, nogreater than about 12 wt. %, no greater than about 11 wt. %, or nogreater than about 10 wt. %; and heating the shaped carbon composite ina heating zone to carbonize the binder thereby producing the shapedporous carbon product.

Still further embodiments are directed to processes for preparing ashaped porous carbon product that comprise mixing water, a carbonaceousmaterial, and an organic binder to form a carbon-binder mixture, whereinthe binder comprises: (i) a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof and (ii) a water solublepolymer, wherein a 2 wt. % aqueous solution or a 5 wt. % aqueoussolution of the water soluble polymer has a viscosity of no greater thanabout 500 mPa·s, no greater than about 400 mPa·s, no greater than about300 mPa·s, no greater than about 200 mPa·s, no greater than about 100mPa·s, no greater than about 75 mPa·s, or no greater than about 50 mPa·sat 25° C. and/or the water soluble polymer has a number averagemolecular weight (M_(n)) that is no greater than about 50,000 g/mol, nogreater than about 40,000 g/mol, no greater than about 30,000 g/mol, nogreater than about 25,000 g/mol, or no greater than about 20,000 g/mol;forming the carbon-binder mixture to produce a shaped carbon composite;and heating the shaped carbon composite in a heating zone to carbonizethe binder thereby producing the shaped porous carbon product.

Further aspects of the present invention are directed to shaped porouscarbon products. In accordance with various embodiments, the shapedporous carbon products comprise carbon black and a carbonized bindercomprising a carbonization product of an organic binder, wherein theshaped porous carbon product has a BET specific surface area from about5 m²/g to about 500 m²/g, a mean pore diameter greater than about 10 nm,a specific pore volume greater than about 0.1 cm³/g, a radial piececrush strength greater than about 4.4 N/mm (1 lb/mm), greater than about8.8 N/mm (2 lbs/mm), greater than about 13.3 N/mm (3 lbs/mm), greaterthan about 15 N/mm (3.4 lbs/mm), greater than about 17 N/mm (3.8lbs/mm), or greater than about 20 N/mm (4.5 lbs/mm), and a carbon blackcontent of at least about 35 wt. %, and wherein the shaped porous carbonproduct has improved wettability as compared to shaped porous carbonproduct control 1 as described herein.

In accordance with other embodiments, the shaped porous carbon productscomprise a carbon agglomerate comprising a carbonaceous material whereinthe shaped porous carbon product has a diameter of at least about 50 μm,a BET specific surface area from about 5 m²/g to about 500 m²/g, a meanpore diameter greater than about 10 nm, a specific pore volume greaterthan about 0.1 cm³/g, and a radial piece crush strength greater thanabout 4.4 N/mm (1 lb/mm), greater than about 8.8 N/mm (2 lbs/mm),greater than about 13.3 N/mm (3 lbs/mm), greater than about 15 N/mm (3.4lbs/mm), greater than about 17 N/mm (3.8 lbs/mm), or greater than about20 N/mm (4.5 lbs/mm), and wherein the shaped porous carbon product hasimproved wettability as compared to shaped porous carbon product control1 as described herein.

Aspects of the present invention are also directed to various catalystcompositions and methods for preparing the catalyst compositions. Forexample, a catalyst composition according to various embodimentscomprises a shaped porous carbon product as a catalyst support and acatalytically active component or precursor thereof at a surface of thesupport. Another catalyst composition comprises a shaped porous carbonsupport and a catalytically active component or precursor thereofcomprising platinum and gold at a surface of the support. Still anothercatalyst composition comprises a shaped porous carbon support and acatalytically active component or precursor thereof comprising platinumand rhodium at a surface of the support. Methods of preparing a catalystcomposition in accordance with the present invention comprise depositinga catalytically active component or precursor thereof on a shaped porouscarbon product.

In other aspects, the present invention is further directed to variousprocesses of using the shaped porous carbon products and the catalystcompositions. One process in accordance with the present invention isfor the catalytic conversion of a reactant comprising contacting aliquid medium comprising the reactant with a catalyst composition of thepresent invention. Other processes include the selective oxidation of analdose to an aldaric acid and the selective hydrodeoxygenation ofaldaric acid or salt, ester, or lactone thereof to a dicarboxylic acid.Moreover, the present invention is directed to methods of preparing areactor vessel for a liquid phase catalytic reaction. The methodscomprise charging the reactor vessel with a catalyst composition of thepresent invention.

Other objects and features will be in part apparent and in part pointedout hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a scanning electron microscopy image of thecross-section of a sample of the catalyst extrudate prepared withMONARCH 700 carbon black.

FIG. 2 provides a magnified view of one of catalyst extrudatecross-sections of FIG. 1.

FIG. 3 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for a raw MONARCH 700 carbon black material.

FIG. 4 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for a fresh catalyst extrudate including the MONARCH700 carbon black material.

FIG. 5 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for a catalyst extrudate including the MONARCH 700carbon black material following 350 hours of use.

FIG. 6 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for an extrudate using MONARCH 700 carbon black and aglucose/hydroxyethyl cellulose binder.

FIG. 7 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for an extrudate using Sid Richardson SC159 carbonblack and a glucose/hydroxyethyl cellulose binder.

FIG. 8 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for an extrudate using Sid Richardson SC 159 carbonblack and a glucose/hydroxyethyl cellulose binder which has been exposedto oxygen at 300° C. for 3 hours.

FIG. 9 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for an extrudate using Asbury 5368 carbon black and aglucose/hydroxyethyl cellulose binder.

FIG. 10 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for an activated carbon extrudate of Sud ChemieG32H-N-75.

FIG. 11 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for an activated carbon extrudate of Donau SupersorbonK4-35.

FIG. 12 presents the pore size distribution for an extrudate using SidRichardson SC159 carbon black and a glucose/hydroxyethyl cellulosebinder measured by mercury porosimetry.

DETAILED DESCRIPTION

The present invention generally relates to shaped porous carbon productsand processes for preparing these products. The shaped porous carbonproducts can be used, for example, as catalyst supports, chromatographicsupport material, filtration media, adsorbents, and the like. Thepresent invention also relates to catalyst compositions including theseshaped porous carbon products, processes of preparing the catalystcompositions, and various processes of using the shaped porous carbonproducts and catalyst compositions.

The present invention provides shaped porous carbon products thatexhibit high mechanical strength and are resistant to crushing andattrition during use. Further, the shaped porous carbon products possessexcellent chemical stability to reactive solvents such as acids andother polar solvents even at elevated temperatures. The shaped porouscarbon products are highly suited for liquid phase catalytic reactionsbecause they can provide for effective mass transfer of compounds havingrelatively large molecular volumes to and away the surface of thesupport.

The present invention also provides processes for preparing the shapedporous carbon products. The shaped porous carbon products can beprepared from inexpensive and readily available materials whichadvantageously improves process economics. Furthermore, the disclosedprocesses are suited for preparation of robust, mechanically strong,shaped porous carbon products through the use of water soluble organicbinders. These processes avoid the use of organic solvents that requirespecial handling and storage.

The present invention further provides catalyst compositions comprisingthe shaped porous carbon products as catalyst supports and processes forpreparing these catalyst compositions. The shaped porous carbon productsexhibit a high degree of retention of the catalytically activecomponent(s) of the catalyst compositions, which beneficially avoids orreduces the amount of catalytically active material leached into aliquid phase reaction medium. Also, the catalyst compositions possess ahigh degree of stability which is necessary for commodity chemicalproduction.

Further, the shaped porous carbon products of the present invention canbe highly wettable, which improves catalyst preparation methods whenthese products are used as catalyst supports. A high wetting rate isadvantageous for catalyst preparation, especially wet catalystpreparation techniques, because it provides for rapid and uniformcontact between the solution containing the catalytically activecomponent or precursor thereof and the pore surfaces of the support. Asa result, the catalytically active component or precursor thereof ismore dispersed on the support, which can lead to higher production ofcatalyst materials. Furthermore, a fast wetting rate limits contact timeunder mixing conditions which can decrease the potential for formationof catalyst fines through attrition and abrasion of the catalyst supportunder mixing conditions.

The present invention also provides processes utilizing shaped porouscarbon products and catalyst compositions, such as for the conversion ofbiorenewably-derived molecules and intermediates for commodityapplications (e.g., the selective oxidation of glucose to glucaric acid)or for applications requiring adsorption of compounds having relativelylarge molecular volumes. Surprisingly, it has been found that the shapedporous carbon products exhibit a superior mechanical strength (e.g.,mechanical piece crush strength and/or radial piece crush strength), andthe use of catalyst compositions comprising the shaped porous carbonproducts of the present invention provides unexpectedly higherproductivity, selectivity and/or yield in certain reactions whencompared to similar catalysts compositions with different catalystsupport materials.

Shaped Porous Carbon Products and Methods of Preparation

Generally, the shaped porous carbon products of the present inventionare prepared with a carbonaceous material. The term, “carbonaceousmaterial” is used herein to refer to elemental carbon that is in theform of graphite or an amorphous form of carbon, and combinationsthereof. Specific examples of amorphous carbonaceous materials includeactivated carbon, carbon black, and combinations thereof. The choice ofcarbonaceous material employed may depend on the properties of theshaped porous carbon product desired. For example, when a relatively lowporosity, low specific surface area product is desired, carbon black istypically employed. When a relatively high porosity, high specificsurface area product is desired, activated carbon is typically utilized.In certain applications, e.g., when a highly electrically-conductiveproduct is desired, graphite may be employed as the carbonaceousmaterial.

In some embodiments, the shaped porous carbon products of the presentinvention are prepared with carbon black as the carbonaceous material.Carbon black materials include various subtypes including acetyleneblack, conductive black, channel black, furnace black, lamp black andthermal black. The primary processes for manufacturing carbon black arethe furnace and thermal processes. Generally, carbon black is producedthrough the deposition of solid carbon particles formed in the gas phaseby combustion or thermal cracking of petroleum products. Carbon blackmaterials are characterized by particles with diameters in the nanometerrange, typically from about 5 to about 500 nm. Carbon black materialscan be supplied as powders or agglomerates of carbon black particles(e.g., pellets and granular forms). Some carbon black agglomerates havea particle size in the range of from about 100 μm to about 1000 μm.

Carbon black materials also have much lower surface areas, a higherconcentration of mesopores, and lower ash and sulfur content whencompared to activated carbons. Carbon black materials are deployedcommercially for many applications such as fillers, pigments,reinforcement materials and viscosity modifiers. However, due to theirvery low surface areas, carbon black materials are not typically used assupports for chemical catalysis or adsorbents. Low surface area carbonblack materials can be considered non-optimal as support structures forcatalytic applications because low surfaces areas are considereddetrimental to effective dispersion of catalytically active componentsleading to poor catalytic activity.

As noted, activated carbons are thought to possess an optimum supportstructure for catalytic applications as they enable good dispersion ofcatalytically active components and effective adsorption and reaction ofchemical reagents at the catalyst surface. In contrast, the use ofcarbon black as a catalyst support has been limited. In order to utilizecarbon blacks as supports for chemical catalysis, several groups havereported methods to modify carbon black materials. Reportedmodifications are centered on methods to increase the surface area ofthe carbon black materials. U.S. Pat. No. 6,337,302 describes a processto render a “virtually useless” carbon black into an activated carbonfor commodity applications. U.S. Pat. No. 3,329,626 describes a processto convert carbon black materials with surface areas from 40-150 m²/g bysteam activation into activated carbons with surface areas up to around1200 m²/g.

Notwithstanding these teachings, it has been surprisingly discoveredthat certain carbon black materials exhibiting particular combinationsof characteristics such as surface area, pore volume, and pore diameterare highly effective for use in shaped porous carbon catalyst supportsfor catalytic reactions including liquid and mixed phase reactionmediums. The shaped porous carbon products of the present invention canbe shaped into mechanically strong, chemically stable, robust forms thatcan reduce resistance to liquid and gas flows, withstand desired processconditions, and provide for long term, stable catalytic operation. Theseshaped porous carbon products provide high productivity and highselectivity during long term continuous flow operation under demandingreaction conditions including liquid phase reactions in which thecatalyst composition is exposed to reactive solvents such as acids andwater at elevated temperatures.

The carbonaceous material typically constitutes a large portion of theshaped porous carbon product of the present invention. As such, thecarbonaceous material (e.g., carbon black) content of the shaped porouscarbon product is at least about 35 wt. % or more such as at least about40 wt. %, at least about 45 wt. %, at least about 50 wt. %, at leastabout 55 wt. %, at least about 60 wt. %, at least about 65 wt. %, or atleast about 70 wt. % on a dry weight basis. In various embodiments, thecarbonaceous material (e.g., carbon black) content of the shaped porouscarbon product is from about 35 wt. % to about 80 wt. %, from about 35wt. % to about 75 wt. %, from about 40 wt. % to about 80 wt. %, or fromabout 40 wt. % to about 75 wt. % on a dry weight basis. The carbonaceousmaterial content of the shaped porous carbon product is determined bythe following formula:

(Weight of carbonaceous material used to prepare the shaped porouscarbon product)/(Dry weight of the shaped porous carbon product)×100%

When carbon black is used as the carbonaceous material, the carbon blackmaterials used to prepare a shaped porous carbon product of the presentinvention typically have a BET specific surface area that is at leastabout 5 m²/g, at least about 7 m²/g, or at least about 10 m²/g. Forexample, the BET specific surface can be in the range of from about 5m²/g to about 500 m²/g, from about 5 m²/g to about 350 m²/g, from about5 m²/g to about 250 m²/g, from about 5 m²/g to about 225 m²/g, fromabout 5 m²/g to about 200 m²/g, from about 5 m²/g to about 175 m²/g,from about 5 m²/g to about 150 m²/g, from about 5 m²/g to about 125m²/g, from about 5 m²/g to about 100 m²/g, from about 7 m²/g to about500 m²/g, from about 7 m ²/g to about 350 m²/g, from about 7 m²/g toabout 250 m²/g, from about 7 m²/g to about 225 m ²/g, from about 7 m²/gto about 200 m²/g, from about 7 m²/g to about 175 m²/g, from about 7m²/g to about 150 m²/g, from about 7 m²/g to about 125 m²/g, from about7 m²/g to about 100 m²/g, from about 10 m²/g to about 500 m²/g, fromabout 10 m²/g to about 350 m²/g, from about 10 m²/g to about 250 m²/g,from about 10 m²/g to about 225 m²/g, from about 10 m ²/g to about 200m²/g, from about 10 m²/g to about 175 m²/g, from about 10 m²/g to about150 m²/g, from about 10 m²/g to about 125 m²/g, or from about 10 m²/g toabout 100 m²/g. In various embodiments, the BET specific surface area ofthe carbon black is in the range of from about 20 m²/g to about 500 m²/gfrom about 20 m²/g to about 350 m²/g, from about 20 m ²/g to about 250m²/g, from about 20 m²/g to about 225 m²/g, from about 20 m²/g to about200 m²/g, from about 20 m²/g to about 175 m²/g, from about 20 m²/g toabout 150 m²/g, from about 20 m²/g to about 125 m²/g, or from about 20m²/g to about 100 m²/g, from about 25 m ²/g to about 500 m²/g, fromabout 25 m²/g to about 350 m²/g, from about 25 m²/g to about 250 m²/g,from about 25 m²/g to about 225 m²/g, from about 25 m²/g to about 200m²/g, from about 25 m²/g to about 175 m²/g, from about 25 m²/g to about150 m²/g, from about 25 m ²/g to about 125 m²/g, from about 25 m²/g toabout 100 m²/g, from about 25 m²/g to about 75 m²/g, from about 30 m²/gto about 500 m²/g, from about 30 m²/g to about 350 m²/g, from about 30m²/g to about 250 m²/g, from about 30 m²/g to about 225 m²/g, from about30 m ²/g to about 200 m²/g, from about 30 m²/g to about 175 m²/g, fromabout 30 m²/g to about 150 m²/g, from about 30 m²/g to about 125 m²/g,from about 30 m²/g to about 100 m²/g, or from about 30 m²/g to about 70m²/g. The specific surface area of carbon black materials is determinedfrom nitrogen adsorption data using the Brunauer, Emmett and Teller(BET) Theory. See J. Am. Chem. Soc. 1938, 60, 309-331 and ASTM TestMethods ASTM 3663, D6556, or D4567 which are Standard Test Methods forTotal and External Surface Area Measurements by Nitrogen Adsorption andare incorporated herein by reference.

The carbon black materials generally have a mean pore diameter greaterthan about 5 nm, greater than about 10 nm, greater than about 12 nm, orgreater than about 14 nm. In some embodiments, the mean pore diameter ofthe carbon black materials used to prepare the shaped porous carbonproduct is in the range of from about 5 nm to about 100 nm, from about 5nm to about 70 nm greater, from 5 nm to about 50 nm, from about 5 nm toabout 25 nm, from about 10 nm to about 100 nm, from about 10 nm to about70 nm greater, from 10 nm to about 50 nm, or from about 10 nm to about25 nm. Such mean pore diameters enable effective transport of reactantmolecules possessing large molecular volumes (such asbiorenewably-derived molecules with 6-carbon atom frameworks) into andout of the pore structure of the catalytically active surface, therebyenabling enhanced activity.

The carbon black materials that can be used to prepare the shaped porouscarbon products of the present invention also generally have specificpore volumes greater than about 0.1 cm³/g, greater than about 0.2 cm³/g,or greater than about 0.3 cm³/g. The specific pore volume of the carbonblack materials can range from about 0.1 cm³/g to about 1 cm³/g, fromabout 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g toabout 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, from about 0.2cm³/g to about 1 cm³/g, from about 0.2 cm³/g to about 0.9 cm³/g, fromabout 0.2 cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g to about 0.7cm³/g, from about 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g toabout 0.5 cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g, fromabout 0.3 cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g to about 0.6cm³/g, or from about 0.3 cm³/g to about 0.5 cm³/g. Carbon blackmaterials with these specific pore volumes provide a volume sufficientto provide uniform wetting and good dispersion of the catalyticallyactive components while enabling sufficient contact between the reactantmolecules and the catalytically active surface. Mean pore diameters andpore volumes are determined in accordance with the procedures describedin E. P. Barrett, L. G. Joyner, P. P. Halenda, J. Am. Chem. Soc. 1951,73, 373-380 (BJH method), and ASTM D4222-03(2008) Standard Test Methodfor Determination of Nitrogen Adsorption and Desorption Isotherms ofCatalysts and Catalyst Carriers by Static Volumetric Measurements, whichare incorporated herein by reference.

Specific examples of commercially available carbon black and carbonblack-containing materials that are suitable for use in the presentinvention include those listed in the following table. The specificsurface area, specific pore volume, and mean pore diameter listed belowwere measured by applicant using the methods described herein.

N₂ BET N₂ BJH N₂ BJH Specific Specific Mean Surface Pore Pore CarbonMaterial Area Volume Diameter Carbon Material Manufacturer (m²/g)(cm³/g) (nm) Asbury 5991 Asbury 7 0.01 9.7 THERMAX Cancarb 7 0.01 16.1FloForm N990 THERMAX Cancarb 8 0.01 9.4 Powder Ultra Pure N991 THERMAXUltra Cancarb 8 0.02 17.7 Pure N990 THERMAX Cancarb 8 0.01 8.7 PowderN991 AROSPERSE 15 Orion 8 0.02 10.4 Lamp Black 101 Orion 20 0.03 8.0MONARCH 120 Cabot 23 0.07 27.7 MONARCH 280 Cabot 30 0.08 17.6 N762Continental Carbon 31 0.10 13.9 Asbury 5345 Asbury 37 0.10 10.7 N550Continental Carbon 38 0.10 11.7 MONARCH 280 Cabot 38 0.08 9.7 N120Continental Carbon 39 0.09 10.0 AROSPERSE Orion 39 0.09 9.3 5-183AENSACO 150G Imerys Graphite & 46 0.10 9.7 Carbon - TIMCAL ENSACO 150GImerys Graphite & 47 0.17 13.6 Carbon - TIMCAL SC119 Sid Richardson 510.14 12.2 ENSACO 250G Imerys Graphite & 56 0.17 16.5 Carbon - TIMCALENSACO 250P Imerys Graphite & 56 0.13 9.3 Carbon - TIMCAL ENSACO 260GImerys Graphite & 63 0.18 10.4 Carbon - TIMCAL ENSACO 250G ImerysGraphite & 64 0.24 14.0 Carbon - TIMCAL ENSACO 250P Imerys Graphite & 670.13 9.6 Carbon - TIMCAL SR311 Sid Richardson 74 0.23 12.6 N330Continental Carbon 77 0.33 17.0 MONARCH 570 Cabot 102 0.30 13.8AROSPERSE 138 Orion 112 0.45 18.7 N234 Continental Carbon 117 0.39 13.6N115 Sid Richardson 128 0.49 16.7 (ground) SC419 Sid Richardson 136 0.5616.8 SR155 Sid Richardson 146 0.87 22.2 HP160 Orion 158 0.87 20.8CONDUCTEX K Columbian 167 0.31 10.6 Ultra Chemicals (Aditya Birla)CONDUCTEX SC Columbian 169 0.33 11.3 Ultra Beads Chemicals (AdityaBirla) MONARCH 700 Cabot 181 0.38 12.1 HIBLACK 50LB Orion 183 0.61 15.4RAVEN 2000 Columbian 187 0.68 14.6 Beads Chemicals (Aditya Birla)HIBLACK 50 L Orion 193 0.66 15.7 HP-160 Degussa 200 MONARCH 700 Cabot206 0.38 10.5 HIBLACK 600 L Orion 208 0.76 15.2 Asbury 5302 Asbury 2110.29 9.9 VULCAN XC72R Cabot 217 0.24 7.5 VULCAN XC72R Cabot 218 0.24 8.1Asbury 5303 Asbury 219 0.23 7.9 SC159 Sid Richardson 222 0.48 11.5 20.4kg (45 lb) bag VULCAN XC72 Cabot 230 0.32 9.4 VULCAN XC72R Cabot 2310.28 7.1 VULCAN XC72 Cabot 231 0.30 8.3 SC159 Sid Richardson 231 0.5212.8 SC159 Sid Richardson 234 0.81 18.2 VULCAN XC72 Cabot 237 0.34 8.2PRINTEX L6 Orion 242 0.33 11.4 RAVEN 2500 Ultra Columbian 247 0.67 12.2Beads Chemicals (Aditya Birla) Asbury 5379 Asbury 271 0.83 16.3 Asbury5368 Asbury 303 0.54 10.2 RAVEN 3500 Columbian 320 0.87 14.5 BeadsChemicals (Aditya Birla) COLOUR BLACK Orion 390 0.91 15.6 FW 2 COLOURBLACK Orion 479 0.83 12.2 FW 200 RAVEN 5000 Ultra Columbian 508 0.65 7.3II Beads Chemicals (Aditya Birla) RAVEN 5000 Ultra Columbian 539 0.576.2 3 Beads Chemicals (Aditya Birla) COLOUR BLACK Orion 546 1.10 11.9 FW255 COLOUR BLACK Orion 567 1.13 12.0 FW 171 RAVEN 7000 Columbian 5770.94 10.7 Beads Chemicals (Aditya Birla) ENSACO 350G Imerys Graphite &739 0.74 5.8 Carbon - TIMCAL PRINTEX XE-2B Orion 1060 1.41 5.9

Certain carbon black materials are known to be electrically conductive.Accordingly, in various embodiments, the shaped porous carbon productcomprises conductive carbon black and in some embodiments, the shapedporous carbon product is electrically conductive. In other embodiments,the shaped porous carbon product comprises nonconductive carbon black.In further embodiments, the shaped porous carbon product comprisesnonconductive carbon black wherein the shaped porous carbon product doesnot exhibit a conductivity that is suitable for a conductive electrode.In certain embodiments, the shaped porous carbon product comprisesnonconductive carbon black and less than about 50%, less than about 40%,less than about 30%, less than about 20%, less than about 10%, less thanabout 5%, or less than about 1% conductive carbon black based on thetotal weight of the carbon black in the shaped porous carbon productand/or the total weight of the carbon black used to prepare the shapedporous carbon product. In some embodiments, the shaped porous carbonproduct comprises carbon black consisting of or consisting essentiallyof nonconductive carbon black. In some embodiments, the carbon blackcomprises a silica-bound or alumina-bound carbon black. In certainembodiments, the shaped porous carbon product can further includegraphite and/or a metal oxide (e.g., alumina, silica, titania, and thelike).

The shaped porous carbon product comprising the carbonaceous material(e.g., carbon black) may be prepared by various methods such as drypowder pressing, drip casting, injection molding, 3D-printing, extrusionand other pelletizing and granulating methods. For example, dry powderpressing involves compressing the carbonaceous material (e.g., carbonblack particles) in a press such as a hot or cold isostatic press or acalandering press. Other pelletizing and granulating methods includetumbling the carbonaceous material and contacting the particles with aspray containing a binder.

Methods of preparing the shaped porous carbon product generally comprisemixing a carbonaceous material and a binder to form a carbon-bindermixture; forming the carbon-binder mixture to produce a shaped carboncomposite; heating the shaped carbon composite in a heating zone tocarbonize the binder thereby producing the shaped porous carbon product.In various embodiments, methods of preparing the shaped porous carbonproduct comprise mixing a solvent such as water, a carbonaceousmaterial, and a binder to form a carbon-binder mixture; forming thecarbon-binder mixture to produce a shaped carbon composite; heating theshaped carbon composite in a heating zone to carbonize the binderthereby producing the shaped porous carbon product.

In some embodiments, methods of preparing the shaped porous carbonproduct comprise mixing water, carbon black, and a binder to form acarbon black mixture; forming the carbon black mixture to produce ashaped carbon black composite; heating the shaped carbon black compositeto carbonize the binder to a water insoluble state and to produce ashaped porous carbon product. In various methods of preparing the shapedporous carbon products, a binder solution can be prepared by mixingwater and the binder prior to mixing with carbon black.

The water content of the carbon-binder mixture (e.g., carbon blackmixture) is typically no more than about 80% by weight, no more thanabout 55% by weight, no more than about 40% by weight, or no more thanabout 25% by weight. In various embodiments, the water content of thecarbon-binder mixture (e.g., carbon black mixture) can be from about 5wt. % to about 70 wt. %, from about 5 wt. % to about 55 wt. %, fromabout 5 wt. % to about 40 wt. %, or from about 5 wt. % to about 25 wt.%.

The viscosity of the binder solution can vary, for example, according tothe binder content and can be readily adjusted to suit a particularshaping process by varying the relative quantities of solid and liquidcomponents. For example, the viscosity of the aqueous solution can bevaried by adjusting the amount of binder and type of binder utilized(binder types may differ with respect to, for example, saccharide type,polymer class, molecular weight, average molecular weight of polymer,molecular weight polydispersity of polymer, etc.). Also in variousmethods, the water and binder can be mixed and heated to form the bindersolution. In some instances, heating can enhance the amount of binderthat can be incorporated into the binder solution and/or carbon-bindermixture (e.g., carbon black mixture) by increasing the solubility of thebinder. For example, the water and binder can be heated to a temperatureof at least about 50° C., at least about 60° C., or at least about 70°C. In various embodiments, the water and binder can be heated to atemperature of from about 50° C. to about 95° C., from about 50° C. toabout 90° C., or from about 60° C. to about 85° C.

After mixing and heating to form the binder solution, the bindersolution can be cooled as needed prior to mixing with the carbonaceousmaterial (e.g., carbon black) or prior to forming the shaped carboncomposite.

One method of preparing the shaped porous carbon product of the presentinvention comprises mixing carbon black particles with a solutioncomprising a binder to produce a slurry; forming the slurry (e.g., byextrusion) to produce a shaped carbon black composite and heating orpyrolyzing the shaped carbon black composite to carbonize the binder toproduce the shaped porous carbon product.

In various methods of preparing the shaped porous carbon product, abinder solution or binder and water are thoroughly mixed and blendedwith the carbonaceous material (e.g., carbon black) to prepare acarbon-binder mixture (e.g., a slurry or a paste). The weight ratio ofbinder to carbonaceous material in the carbon-binder mixture (e.g.,carbon black in the carbon black mixture) is typically at least about1:4, at least about 1:3, at least about 1:2, at least about 1:1, or atleast 1.5:1. In some embodiments, the weight ratio of binder tocarbonaceous material in the carbon-binder mixture (e.g., carbon blackin the carbon black mixture) is no more than about 1:4, no more thanabout 1:5, or no more than about 1:10. The weight ratio of binder tocarbonaceous material in the carbon-binder mixture (e.g., carbon blackin the carbon black mixture) can also be from about 1:10 to about 3:1,from about 1:10 to about 1:1, from about 1:10 to about 1:4, from about1:4 to about 3:1, from about 1:4 to about 1:1, from about 1:3 to about2:1, from about 1:3 to about 1:1, or about 1:1.

Typically, the carbonaceous material in the carbon-binder mixture (e.g.,carbon black in the carbon black mixture) is at least about 35 wt. % ormore such as at least about 40 wt. %, at least about 45 wt. %, as atleast about 50 wt. %, as at least about 55 wt. %, at least about 60 wt.%, at least about 65 wt. %, at least about 70 wt. %, at least about 75wt. %, at least about 80 wt. %, at least about 85 wt. %, or at leastabout 90 wt. % on a dry weight basis. In various embodiments, thecarbonaceous material in the carbon-binder mixture (e.g., carbon blackin the carbon black mixture) is from about 35 wt. % to about 90 wt. %,from about 35 wt. % to about 80 wt. %, from about 35 wt. % to about 75wt. %, from about 40 wt. % to about 90 wt. %, from about 40 wt. % toabout 80 wt. %, from about 40 wt. % to about 75 wt. %, from about 35 wt.% to about 50 wt. %, from about 38 wt. % to about 48 wt. %, or fromabout 45 wt. % to about 50 wt. % on a dry weight basis. Also, the bindercontent of the carbon-binder mixture (e.g., carbon black mixture) istypically at least about 5 wt. %, at least about 10 wt. %, at leastabout 20 wt. %, at least about 25 wt. %, at least about 30 wt. %, atleast about 35 wt. %, at least about 40 wt. %, at least about 45 wt. %,at least about 50 wt. %, at least about 55 wt. %, at least about 60 wt.%, or at least about 65 wt. % on a dry weight basis. In various methodsfor preparing the shaped porous carbon product of the present inventionas described herein, the binder content of the carbon-binder mixture(e.g., carbon black mixture) is from about 5 wt. % to about 65 wt. %,from about 5 wt. % to about 50 wt. %, from about 5 wt. % to about 45 wt.%, from about 10 wt. % to about 65 wt. %, from about 10 wt. % to about50 wt. %, from about 10 wt. % to about 45 wt. %, from about 15 wt. % toabout 50 wt. %, from about 20 wt. % to about 65 wt. %, from about 20 wt.% to about 50 wt. %, from about 20 wt. % to about 45 wt. %, from about30 wt. % to about 65 wt. %, from about 30 wt. % to about 60 wt. %, fromabout 35 wt. % to about 65 wt. %, from about 40 wt. % to about 65 wt. %,from about 50 wt. % to about 65 wt. %, or from about 50 wt. % to about65 wt. % on a dry weight basis.

Various methods of preparing the shaped porous carbon products canfurther comprise pressing or kneading the carbon-binder mixture (e.g.,carbon black mixture). Pressing or kneading the carbon-binder mixturecompacts the mixture and can reduce the water content of the mixture.Pressing or kneading of the water, carbonaceous material, and binder(e.g., carbon black mixture) can be conducted simultaneously with themixing of the water, carbonaceous material and binder. For example, onemethod of mixing the water, carbonaceous material, and binder andsimultaneously pressing the resulting carbon-binder mixture can beconducted using a mixer muller.

After mixing of the carbonaceous material and binder, the resultingcarbon-binder mixture is formed into a shaped carbon composite structureof the desired shape and dimensions by a forming technique such asextrusion, pelletizing, pilling, tableting, cold or hot isostaticpressing, calandering, injection molding, 3D printing, drip casting, orother methods known to produce shaped structures. Forming methods suchas cold or hot isostatic pressing and 3D printing may or may not requirea binder.

In general, the shaped porous carbon product can be shaped and sized foruse in known industrial reactor formats such as batch slurry, continuousslurry-based stirred tank reactors, fixed beds, ebulated beds and otherknown industrial reactor formats. The shaped porous carbon product maybe formed into various shapes including spheres, beads, cylinders,pellets, multi-lobed shapes, rings, stars, ripped cylinders, triholes,alphas, wheels, etc. Also, the shaped porous carbon product may beformed into amorphous, non-geometric, and random shapes as well asunsymmetrical shapes like hi-flow rings and cones and alpha-rings. Themean diameter of the shaped porous carbon product is typically at leastabout 50 μm (0.05 mm), at least about 500 μm (0.5 mm), at least about1,000 μm (1 mm), at least about 10,000 μm (10 mm) or larger toaccommodate process requirements.

For extrusion forming, a pressure of at least about 100 kPa (1 bar), atleast about 1,000 kPa (10 bar), at least about 3,000 kPa (30 bar), atleast about 4,000 kPa (40 bar) or between about 100 kPa (1 bar) to about10,000 kPa (100 bar), between about 1,000 kPa (10 bar) to about 5,000kPa (50 bar), between 500 kPa (5 bar) and 5,000 kPa (50 bar), or between1,000 kPa (10 bar) and 3,000 kPa (30 bar) is typically applied to thecarbon-binder mixture (e.g., carbon black mixture).

In drip casting methods, the carbon-binder mixture (e.g., carbon blackmixture comprising carbon black particles and the binder) are dispensedas droplets into a casting bath to form the shaped carbon composite,which is then separated from the casting bath. Carbon-binder mixturedroplets of a tailored diameter may be dispensed through a sized nozzleand dropped into a bath to produce solidified, spherically-shaped carboncomposites of various diameters. In various embodiments of this method,the binder comprises an alginate (or alginate in combination withanother carbohydrate binder as described herein) which can be dispensedinto a bath containing a reagent to cause solidification such as anionic salt (e.g., calcium salt) as described in U.S. Pat. No. 5,472,648,the entire contents of which are incorporated herein by reference. Thedroplets are subsequently allowed to remain substantially free in theionic solution until the required degree of solidification andconsolidation has been attained. Alternatively, the drip casting bathutilized may be, for example, an oil bath, or a bath to cause freezedrying. When an oil bath is used, the temperature of the oil issufficiently high that the binder is thermally set (e.g., causes thebinder to convert to a three-dimensional gel). When a freeze drying bathis used, the resultant beads are typically dried by vacuum treatment.The shaped carbon composites resulting from such dip casting methods aresubsequently pyrolyzed.

As described in further detail below, other components can be added tothe carbon-binder mixture (e.g., carbon black mixture) to assist withthe shaping process (e.g., lubricants, compatibilizers, etc.) or toprovide other benefits. In various embodiments, the carbon-bindermixture further comprises a forming adjuvant. For example, the formingadjuvant can comprise a lubricant. Suitable forming adjuvants include,for instance, lignin or lignin derivatives.

Further, porogens may be mixed with the carbonaceous material and binderto modify and attain the desired pore characteristics in the shapedporous carbon product. Other methods of modifying the porosity of theshaped porous carbon product include mixing two or more differentcarbonaceous starting materials (e.g., carbon blacks having differentshape and/or size that pack irregularly resulting in multimodal poresize distributions, or carbon blacks from different sources/suppliers,or mixing carbon black powders carbon). Other methods of modifying theporosity of the shaped porous carbon product include multiple thermalprocessing and/or multiple compounding (e.g., pyrolysis of a shapedcarbon black composite of carbon powder and binder, then mixing withfresh carbon black powder and binder and pyrolyzing the resultantcomposite again).

In various methods of preparing the shaped porous carbon product, afterprocessing the carbon-binder mixture (e.g., a slurry or a paste) intothe shaped carbon composite, the composite may be dried to remove atleast a portion of the solvent contained therein (e.g., to dehydrate thecomposite). Drying may be achieved by heating the composite atatmospheric pressure and temperatures typically of from about roomtemperature (e.g., about 20° C.) to about 150° C., from about 40° C. toabout 120° C., or from about 60° C. to about 120° C. Other methods ofdrying may be utilized including vacuum drying, freeze drying, anddesiccation. When using certain preparation methods for forming (e.g.,tableting, pressing), no drying step may be required.

In certain instances, it has been found that the drying conditions ofthe shaped carbon composite can affect the mechanical strength of theshaped porous carbon product. In particular, it has been found that whenthe shaped carbon composite is dried relatively fast at highertemperatures (e.g., greater than about 90° C.), then the resultingshaped porous carbon product (following carbonization of the binder) hasa mechanical strength that is further improved when compared to aproduct prepared under relatively slow drying conditions. Without beingbound by theory, applicants propose that relatively fast dryingconditions may prevent or reduce migration of the binder components tothe surface of the carbonaceous material. It is believed that preventingor reducing this migration of the binder components may contribute toeven further enhancement to mechanical strength of the shaped porouscarbon product, as compared to a product prepared under relatively slowdrying conditions at lower temperatures (e.g., less than 90° C.).

Accordingly, various processes of the present invention for preparing ashaped porous carbon product can comprise drying the shaped carboncomposite quickly at elevated temperatures. In these embodiments,processes for preparing a shaped porous carbon product can comprisedrying the shaped carbon composite at a temperature from about 90° C. toabout 175° C., from about 90° C. to about 150° C., from about 100° C. toabout 150° C., or from about 100° C. to about 140° C. Drying at anelevated temperature within these ranges advantageously reduces the timenecessary to achieve a sufficiently dried shaped carbon composite.

Typically, the water content of the shaped carbon composite after dryingis no greater than about 25 wt. %, no greater than about 20 wt. %, nogreater than about 15 wt. %, no greater than about 12 wt. %, no greaterthan about 11 wt. %, or no greater than about 10 wt. %. For example, thewater content of the shaped carbon composite after drying can be fromabout 2 wt. % to about 25 wt. %, from about 2 wt. % to about 20 wt. %,from about 2 wt. % to about 15 wt. %, from about 2 wt. % to about 12 wt.%, from about 2 wt. % to about 11 wt. %, from about 2 wt. % to about 10wt. %, from about 4 wt. % to about 15 wt. %, from about 4 wt. % to about12 wt. %, from about 4 wt. % to about 11 wt. %, from about 4 wt. % toabout 10 wt. %, from about 5 wt. % to about 15 wt. %, from about 5 wt. %to about 12 wt. %, from about 5 wt. % to about 11 wt. %, or from about 5wt. % to about 10 wt. %. Also, in various embodiments, drying can beconducted over a period of time that is no more than about 120 minutes,no more than about 90 minutes, no more than about 75 minutes, no morethan about 60 minutes, no more than about 45 minutes, no more than about30 minutes, or no more than about 20 minutes. For instance, drying canbe conducted over a period of time that is from about 30 minutes toabout 120 minutes, from about 30 minutes to about 90 minutes, from about30 minutes to about 75 minutes, from about 30 minutes to about 60minutes, from about 30 minutes to about 45 minutes, from about 60minutes to about 120 minutes, from about 60 minutes to about 90 minutes,from about 20 minutes to about 60 minutes, or from about 20 minutes toabout 45 minutes.

In some processes of preparing the shaped porous carbon product, it hasbeen found that the time elapsed between drying and the carbonizationstep can affect the mechanical strength of the shaped porous carbonproduct. In some instances, when the shaped carbon composite is storedfor a significant amount of time before carbonization, then themechanical strength of the shaped porous carbon product is lower ascompared to a shaped carbon composite that is immediately or almostimmediately introduced to the carbonization step. Applicants haveunexpectedly found that drying the shaped carbon composite to a watercontent of about 11 wt. % or less provides for a shaped porous carbonproduct that has enhanced mechanical strength (e.g., a radial piececrush strength that is greater than about 8.8 N/mm (2 lbs/mm)) even ifthe shaped carbon composite is not immediately carbonized followingdrying.

Drying can be conducted using a technique that can effect rapid drying.For example, drying can be performed using a continuous belt dryer. Inbelt drying, temperatures and residence time can be adjusted to providea dried shaped carbon composite having the reduced water contentsspecified herein.

Following forming and drying, the shaped carbon composite is heated in aheating zone to carbonize the binder (e.g., pyrolyze) thereby producingthe shaped porous carbon product. In various methods of preparing theshaped porous carbon product, the shaped carbon composite (e.g.,resulting from extrusion, pelletizing, pilling, tableting, cold or hotisostatic pressing, calandering, injection molding, 3D printing, dripcasting, and other forming methods) is heated in an inert (e.g., aninert nitrogen atmosphere), oxidative, or reductive atmosphere tocarbonize at least a portion of the binder to a water insoluble stateand produce a shaped porous carbon product. Preferably, heating isconducted in an inert atmosphere.

Generally, the shaped carbon composite is heated to a final temperatureof at least about 400° C., at least about 500° C., at least about 600°C., at least about 700° C., or at least about 800° C. in the heatingzone. Heating can be conducted at a temperature of from about 250° C. toabout 1,000° C., from about 300° C. to about 900° C., from about 300° C.to about 850° C., from about 300° C. to about 800° C., from about 350°C. to about 850° C., from about 350° C. to about 800° C., from about350° C. to about 700° C., from about 400° C. to about 850° C. or fromabout 400° C. to about 800° C. In various embodiments, the shaped carboncomposite is heated to a final temperature of from about 400° C. toabout 1,000° C., from about 400° C. to about 900° C., from about 400° C.to about 850° C., from about 400° C. to about 800° C., from about 500°C. to about 850° C., from about 500° C. to about 800° C., from about500° C. to about 700° C., from about 600° C. to about 850° C. or fromabout 600° C. to about 800° C. in the heating zone.

The heating zone can include a single or multiple heating stages. Invarious embodiments, the heating zone comprises at least two heatingstages that are each maintained at an approximately constant temperature(e.g., ±5-10° C.) and the temperature of each stage differs by at leastabout 50° C., at least about 100° C., at least about 150° C., at leastabout 200° C., at least about 250° C., at least about 300° C., at leastabout 350° C., or at least about 400° C. with the temperature increasingfrom one stage to the next. In some embodiments, the heating zonecomprises at least three, at least four, at least five, or at least sixheating stages that are each maintained at an approximately constanttemperature and the temperature of each stage independently differs byat least about 50° C., at least about 100° C., at least about 150° C.,at least about 200° C., at least about 250° C., at least about 300° C.,at least about 350° C., or at least about 400° C. from the precedingstage. In various embodiments, the temperature of each stage differs byfrom about 50° C. to about 500° C., from about 100° C. to about 500° C.,from about 200° C. to about 500° C., from about 300° C. to about 500°C., from about 50° C. to about 400° C., from about 100° C. to about 400°C., from about 150° C. to about 400° C., from about 200° C. to about400° C., from about 300° C. to about 400° C., from about 50° C. to about300° C., from about 100° C. to about 300° C., from about 150° C. toabout 300° C., or from about 200° C. to about 300° C.

In certain embodiments the heating zone comprises: (1) a first heatingstage where the shaped carbon composite is heated at a firsttemperature; and (2) a second heating stage where the shaped carboncomposite is heated at a second temperature. In these embodiments, thefirst and second temperature are each approximately constant and thesecond temperature is greater than the first temperature by at leastabout 50° C., at least about 100° C., at least about 150° C., at leastabout 200° C., at least about 250° C., at least about 300° C., at leastabout 350° C., or at least about 400° C. For example, the temperature ofthe first heating stage temperature and the second stage heating stagecan differ by from about 50° C. to about 500° C., from about 100° C. toabout 500° C., from about 200° C. to about 500° C., from about 300° C.to about 500° C., from about 50° C. to about 400° C., from about 100° C.to about 400° C., from about 150° C. to about 400° C., from about 200°C. to about 400° C., from about 300° C. to about 400° C., from about 50°C. to about 300° C., from about 100° C. to about 300° C., from about150° C. to about 300° C., or from about 200° C. to about 300° C.

In further embodiments, the heating zone comprises a third heating stagewhere the shaped carbon composite is heated at a third temperature thatis approximately constant and is greater than the second heating stagetemperature by at least about 50° C., at least about 100° C., at leastabout 150° C., at least about 200° C., at least about 250° C., at leastabout 300° C., at least about 350° C., or at least about 400° C. Forexample, the temperature of the second heating stage temperature and thethird stage heating stage temperature can differ by from about 50° C. toabout 500° C., from about 100° C. to about 500° C., from about 200° C.to about 500° C., from about 300° C. to about 500° C., from about 50° C.to about 400° C., from about 100° C. to about 400° C., from about 150°C. to about 400° C., from about 200° C. to about 400° C., from about300° C. to about 400° C., from about 50° C. to about 300° C., from about100° C. to about 300° C., from about 150° C. to about 300° C., or fromabout 200° C. to about 300° C.

When a continuous process for producing the shaped porous carbon productis desired, then the heating zone can be within a continuous rotary kilnor belt conveyor furnace. As noted, various embodiments include the useof a heating zone comprising multiple heating stages. Thus, in theseinstances, a multi-stage continuous rotary kiln or belt conveyor furnacecan be used to heat the shaped carbon composite.

The heating zone can further include one or more stages for drying theshaped carbon composite prior to carbonization. In other words, thedrying step and carbonization step can be conducted in a heating zonecomprising a series of heating stages (multi-stage heating zone) inwhich at least the first heating stage (e.g., one, two, or three heatingstages for drying) is at a temperature suitable for drying, such as inthe range of from about 90° C. to about 175° C., from about 90° C. toabout 150° C., from about 100° C. to about 150° C., or from about 100°C. to about 140° C. Carbonization of at least a portion of the binder toproduce the shaped porous carbon product can be completed in highertemperature heating stages that are subsequent to those for drying.These higher temperature stages can be operated as previously discussed.A belt conveyor furnace is one type of furnace suitable for amulti-stage heating zone that can be adapted to include one or morestages for drying and one or more higher temperature stages forcarbonization of the binder.

In some instances and depending upon the binder employed, it has beendetermined that lower carbonization temperatures can lead to slowleaching of the remnants of the binder from the shaped porous carbonproduct which reduces mechanical strength over extended periods of usein catalytic reactions. Generally, to ensure longer term stability, theheat treatment is conducted at higher carbonization temperatures withinthe ranges specified above. In some instances, the resultant shapedporous carbon product may be washed after the heat treatment to removeimpurities.

In accordance with various preparation methods, shaped porous carbonproducts of the present invention comprise a binder or carbonizationproduct thereof in addition to the carbonaceous material (e.g., carbonblack). Various references, including U.S. Pat. No. 3,978,000, describethe use of acetone soluble organic polymers and thermosetting resin asbinders for shaped carbon supports. However, the use of flammableorganic solvents and expensive thermosetting resins is not desirable oreconomical for manufacturing large quantities of shaped porous carbonproduct.

Mechanically-strong, shaped porous carbon products of the invention canbe prepared by the use of an effective binder. The use of an effectivebinder provides a robust shaped porous carbon product capable ofwithstanding the prevailing conditions within continuous liquid phaseflow environments such as in conversions of biorenewably-derivedmolecules or intermediates in which the liquid phase may contain wateror acidic media. In such instances the shaped porous carbon product ismechanically and chemically stable to enable long-term operation withoutsignificant loss in catalyst performance. Moreover, the use of aneffective binder provides a robust shaped porous carbon product capableof withstanding elevated temperatures.

Applicants have found that readily available water soluble organiccompounds are suitable binders for the preparation of mechanicallystrong shaped porous carbon products. As used in herein, a binder isdeemed water soluble if the solubility at 50° C. is at least about 1 wt.%, preferably at least about 2 wt. %. Aqueous solutions of organicbinders are highly amenable to commercial manufacturing methods. Organicbinders that dissolve in aqueous solutions enable good mixing anddispersion when contacted with the carbonaceous materials (e.g., carbonblack). These binders also avoid safety and processing issues associatedwith large-scale use of organic solvents which may be flammable andrequire special storage and handling. Also, these binders are relativelyinexpensive when compared to costly polymer-based binders. As such, invarious embodiments, the carbon-binder mixtures (e.g., carbon blackmixtures) do not contain water immiscible solvents.

However, in some embodiments, a solvent in addition to or in place ofwater can be used. For example, water-miscible solvents such as ethyleneglycol, glycerol, lactic acid, and mixtures thereof can replace in itsentirety or at least a portion of the water. In certain embodiments, thesolvent is free or substantially free of water (e.g., the water contentof the carbon-binder mixture is typically no more than about 5% byweight, no more than about 2% by weight, no more than about 1% byweight, or no more than about 0.1% by weight. In other embodiments, thecarbon-binder mixture is prepared without a solvent (e.g., thecarbon-binder mixture is solvent-free or substantially free of solvent).

Generally, water soluble organic binders can include carbohydrates orderivatives thereof, which may be a monomeric or oligomeric or polymericcarbohydrate (also known as saccharides, oligosaccharide andpolysaccharides). Derivatives of carbohydrates (in monomeric oroligomeric polymeric forms) are also included wherein a functional groupor groups bound to the carbohydrate may be exchanged or derivatized.Such derivatives may be acidic or charged carbohydrates such as alginicacid or alginate salts, or pectin, or aldonic acids, aldaric acids,uronic acids, xylonic or xylaric acids (or oligomers, or polymers orsalts thereof). Other derivatives include sugar alcohols and polymericforms thereof (e.g., sorbitol, mannitol, xylitol or polyols derived fromcarbohydrates). The carbohydrate binder may be used in the form ofsyrups such as molasses or corn syrups or soluble starches or solublegum or modified versions thereof.

In various embodiments, the binder comprises: (i) a saccharide selectedfrom the group consisting of a monosaccharide, a disaccharide, anoligosaccharide, a derivative thereof, and any combination thereofand/or (ii) a water soluble polymer. In some embodiments, the watersoluble organic binder comprises a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof. For example, in certainembodiments, the water soluble organic binder comprises amonosaccharide. The monosaccharide can be selected from the groupconsisting of glucose, fructose, hydrates thereof, syrups thereof (e.g.,corn syrups, molasses, and the like) and combinations thereof. Onepreferred monosaccharide is glucose. In further embodiments, the watersoluble organic binder comprises a disaccharide. Disaccharides includefor example, maltose, sucrose, syrups thereof, and combinations thereof.Saccharides that have been peptized can also be used.

The binder can comprise a water soluble polymer. In various instances,it has been found that water soluble polymers capable of yieldingrelatively low viscosities solutions and/or low molecular weight (i.e.,number average molecular weight) provide a shaped porous carbon producthaving enhanced mechanical strength. Accordingly, in variousembodiments, the binder comprises a water soluble polymer, wherein a 2wt. % aqueous solution or a 5 wt. % aqueous solution of the watersoluble polymer has a viscosity of no greater than about 500 mPa·s, nogreater than about 400 mPa·s, no greater than about 300 mPa·s, nogreater than about 200 mPa·s, no greater than about 100 mPa·s, nogreater than about 75 mPa·s, or no greater than about 50 mPa·s at 25° C.and/or the water soluble polymer has a number average molecular weight(M_(n)) that is no greater than about 50,000 g/mol, no greater thanabout 40,000 g/mol, no greater than about 30,000 g/mol, no greater thanabout 25,000 g/mol, or no greater than about 20,000 g/mol. In someembodiments, the binder comprises a water soluble polymer, wherein a 2wt. % aqueous solution or a 5 wt. % aqueous solution of the watersoluble polymer has a viscosity that is from about 2 to about 500 mPa·s,from about 2 to about 400 mPa·s, from about 2 to about 300 mPa·s, fromabout 2 to about 200 mPa·s, from about 2 to about 150 mPa·s, from about2 to about 100 mPa·s, from about 2 to about 75 mPa·s, or from about 2 toabout 50 mPa·s at 25° C. In these and other embodiments, the watersoluble polymer can have a number average molecular weight (M_(n)) thatis from about 2,000 to about 50,000 g/mol, from about 5,000 to about40,000 g/mol, from about 5,000 to about 30,000 g/mol, from about 5,000to about 25,000 g/mol, from about 5,000 to about 20,000 g/mol, fromabout 10,000 to about 50,000 g/mol, from about 10,000 to about 40,000g/mol, from about 10,000 to about 30,000 g/mol, from about 10,000 toabout 25,000 g/mol, or from about 10,000 to about 20,000 g/mol.

In some instances, it has been discovered that a relatively small amountof the water soluble polymer provides enhanced mechanical strength tothe shaped porous carbon product. Accordingly, in various embodiments,the water soluble polymer can constitute no more than about 5 wt. %, nomore than about 4 wt. %, no more than about 3 wt. %, or no more thanabout 2 wt. % based on the weight of the water, saccharide, and watersoluble polymer mixed with the carbonaceous material. In someembodiments, the water soluble polymer can constitute from about 0.5 wt.% to about 5 wt. %, from about 0.5 wt. % to about 4 wt. %, from about0.5 wt. % to about 3 wt. %, from about 0.5 wt. % to about 2 wt. %, fromabout 1 wt. % to about 5 wt. %, from about 1 wt. % to about 4 wt. %,from about 1 wt. % to about 3 wt. %, or from about 1 wt. % to about 2wt. % based on the weight of the water, and saccharide, and watersoluble polymer mixed with the carbonaceous material.

Suitable water soluble polymers include various polymeric carbohydrates,derivatives of polymeric carbohydrates, non-carbohydrate syntheticpolymers, or any combination thereof. For example, polymericcarbohydrates or derivatives of the polymeric carbohydrates can comprisecellulosic compounds. Cellulosic compounds include, for example,methylcellulose, ethylcellulose, ethylmethylcellulose,hydroxyethylcellulose, hydroxypropylcellulose,methylhydroxyethylcellulose, ethylhydroxyethylcellulose,hydroxypropylmethylcellulose, carboxymethylcellulose, and mixturesthereof. One preferred cellulosic compound is hydroxyethylcellulose.

Further, the polymeric carbohydrate or derivative of the polymericcarbohydrate derivative can be selected from the group consisting ofalginic acid, pectin, aldonic acids, aldaric acids, uronic acids, sugaralcohols, and salts, oligomers, and polymers thereof. The polymericcarbohydrate or derivative of the polymeric carbohydrate can alsocomprise a starch or a soluble gum.

In various embodiments, the binder comprises a non-carbohydratesynthetic polymer. Water soluble polymers or copolymers may be used asbinders. For example, polyacrylic acid, polyvinyl alcohols,polyvinylpyrrolidones, polyvinyl acetates, polyacrylates, polyethers(such as, for example, polyethyelene glycol and the like) and copolymers(which can be block copolymers comprising a water insoluble blockmonomers and water soluble block monomers) derived therefrom, and blendsthereof. In some instances, the water soluble copolymer may be a blockcopolymer comprising a water soluble polymer block and a second polymerblock which may be hydrophobic and amenable to carbonization (e.g.,polystyrene). In another embodiment, polymer dispersions in water areused as binders, i.e., non-water soluble polymers dispersed in water(with the aid of surfactants) such as commercial polyvinyl alcohol,polyacrylonitrile, polyacrylonitrile-butadiene-styrene, phenolic polymeror lignin polymer dispersions. Also copolymers consisting of awater-soluble branch (e.g., polyacrylic acid) and a hydrophobic branch(e.g., polymaleic anhydride, polystyrene) enabling water solubility ofthe copolymer and enabling carbonization of the hydrophobic branchwithout depolymerisation upon pyrolysis. Carbohydrates or derivativesthereof, water soluble polymers and polymer dispersions in water may beused together in various combinations.

Binders comprising a combination of a saccharide and water solublepolymer have been found to provide shaped porous carbon productsexhibiting enhanced mechanical strength. Accordingly, in variousembodiments, the water soluble organic binder comprises: (i) asaccharide selected from the group consisting of a monosaccharide, adisaccharide, an oligosaccharide, a derivative thereof, and anycombination thereof and (ii) a water soluble polymer (e.g., a polymericcarbohydrate, a derivative of a polymeric carbohydrate, or anon-carbohydrate synthetic polymer, or any combination thereof). Theweight ratio of (i) the saccharide to (ii) water soluble polymer (e.g.,the polymeric carbohydrate, derivative of the polymeric carbohydrate, orthe non-carbohydrate synthetic polymer, or combination thereof) can befrom about 5:1 to about 100:1, from about 5:1 to about 50:1, 10:1 toabout 40:1, from about 10:1 to about 30:1, from about 10:1 to about25:1, from about 10:1 to about 20:1, from about 20:1 to about 30:1, orfrom about 25:1 to about 30:1.

As described above, water soluble organic binders that may be used incombination with the saccharide binders include water soluble cellulosesand starches (e.g., hydroxyethylcellulose, hydroxypropylcellulose,hydroxyethylmethylcellulose, hydroxylpropylmethylcellulose,carboxymethylcellulose), water soluble alcohols (e.g., sorbitol,xylitol, polyvinyl alcohols), water soluble acetals (e.g.,polyvinylbutyral), water soluble acids (e.g., stearic acid, citric acid,alginic acid, aldonic acids, aldaric acids, uronic acids, xylonic orxylaric acids (or oligomers, or polymers or salts or esters thereof)polyvinyl acrylic acids (or salts or esters thereof). In someembodiments, the combination of water soluble organic binders comprisesa cellulosic compound and a monosaccharide. In certain embodiments, thecellulosic compound comprises hydroxyethylcellulose, or methylcelluloseand the monosaccharide comprises a glucose, fructose or hydrate thereof(e.g., glucose). In particular, one combination comprises glucose andhydroxyethylcellulose, which provides shaped porous carbon products withenhanced mechanical strength, particularly when processed at highcarbonization temperatures. In other embodiments the combination ofwater soluble organic binders comprises a monosaccharide and awater-soluble alcohol such as sorbitol, mannitol, xylitol or a polyvinylalcohol. In other embodiments, the combination of water soluble organicbinders comprises a monosaccharide, and a water-soluble acid such asstearic acid, pectin, alginic acid or polyacrylic acid (or saltsthereof). In further embodiments, the combination of water solubleorganic binders comprises a monosaccharide and a water-soluble estersuch as a polyacrylate or polyacetate. In still other embodiments, thecombination of water soluble organic binders comprises a monosaccharideand a water-soluble acetal such as a polyacetal (e.g.,polyvinylbutyral).

Other water soluble compounds may be used in combination with acarbohydrate or polymeric binder. Combining a carbohydrate or otherbinder with selected other water soluble organic compounds can provideadvantages in the preparation of and in the properties of the resultantshaped porous carbon product. For example, water soluble organiccompounds such as stearic acid or stearates such as Zr or NH₄ stearatecan provide lubrication during the forming process. Wetting agents maybe added (e.g., GLYDOL series available commercially from Zschimmer andSchwarz).

Porogens may also be added in combination with the binder (or binders).Porogens are typically added to occupy a specific molecular volumewithin the formulation such that after the shaping and thermalprocessing the porogen will be pyrolyzed leaving pores of a certainvolume and diameter within the shaped product. The presence of suchpores can be beneficial to performance. For example, when used as acatalyst support the presence of such pores can lead to more efficientdiffusion (of reactants and products) to and from the catalyticallyactive surfaces. More efficient access and egress for the reactants andproducts can lead to improvements in catalyst productivity andselectivity. Porogens are typically oligomeric (e.g., dimer, trimers ofhigher order oligomers) or polymeric in nature. Water soluble organiccompounds such as water soluble linear and branched polymers andcross-linked polymers are suitable for use as porogens. Polyacrylates(such as weakly cross-linked polyacrylates known as superabsorbers),polyvinyl alcohols, polyvinylacetates, polyesters, polyethers, orcopolymers (which may be block copolymers) thereof may be used asporogens. In some instances, the water soluble copolymer may be a blockcopolymer comprising a water soluble polymer block and a second polymerblock which may be hydrophobic and amenable to carbonization (e.g.,polystyrene). In another embodiment, polymer dispersions in water areused as binders, i.e., non-water soluble polymers dispersed in water(with the aid of surfactants) such as commercial polyvinyl alcohol,polyacrylonitrile, polyacrylonitrile-butadiene-styrene, phenolic polymerdispersions. Also copolymers consisting of a water-soluble branch (e.g.,polyacrylic acid) and a hydrophobic branch (e.g., polymaleic anhydride,polystyrene) enabling water solubility of the copolymer and enablingcarbonization of the hydrophobic branch without depolymerisation uponpyrolysis. Carbohydrates or derivatives thereof, (disaccharides,oligosaccharides, polysaccharides such as sucrose, maltose, trihalose,starch, cellubiose, celluloses), water soluble polymers and polymerdispersions in water may be used together in any combination as aporogen to attain a shaped porous carbon product having the desired poresize and volume characteristics described herein.

Porogens can also be added as gels (e.g., pre-gelated superabsorber) orwater insoluble incompressible solids (e.g., polystyrene microbeads,lignins, phenolic polymers) or expandable porogens such as EXPANSELmicrospheres available from Akzo Nobel Pulp and Performance (Sundsvall,Sweden). The molecular weight of the oligomer or polymer can be alsochosen to design a desired pore sizes and volume characteristics of theshaped carbon product of the invention. For example the desired shapedcarbon product may have a monomodal, bimodal or multimodal pore sizedistribution as a consequence of addition of a porogen. Forillustration, a bimodal or multimodal pore size distribution may consistof a high percentage of pores between 10 and 100 nm and additionally thepresence of pores >100 nm. Such a pore structure may provide performanceadvantages. For example, the presence of such a pore size distributioncan lead to more efficient diffusion (of reactants and products) throughthe larger pore (transport pores) to and from catalytically activesurfaces which reside in the pores sized between 10 and 100 nm. Moreefficient access and egress for the reactants and products can lead toimprovements in catalyst productivity, selectivity, and/or yield.

Following heat treatment of the shaped carbon composite, the resultingshaped porous carbon product comprises the carbonaceous material (e.g.,carbon black) and carbonized binder. More generally, the shaped porouscarbon product can comprise a carbon agglomerate. Without being bound byany particular theory, it is believed that the carbon agglomeratecomprises carbon aggregates or particles that are physically bound orentangled at least in part by the carbonized binder. Moreover, andwithout being bound by any particular theory, the resulting agglomeratemay include chemical bonding of the carbonized binder with the carbonaggregates or particles.

The carbonized binder comprises a carbonization product of a watersoluble organic binder as described herein. Carbonizing the binderduring preparation of the shaped porous carbon product will reduce theweight of the shaped carbon composite from which it is formed.Accordingly, in various embodiments, the carbonized binder content ofthe shaped porous carbon product on a dry weight basis is from about 5wt. % to about 65 wt. %, from about 5 wt. % to about 60 wt. %, fromabout 5 wt. % to about 50 wt. %, from about 5 wt. % to about 40 wt. %,from about 5 wt. % to about 30 wt. %, from about 10 wt. % to about 65wt. %, from about 10 wt. % to about 60 wt. %, from about 10 wt. % toabout 50 wt. %, from about 10 wt. % to about 40 wt. %, from about 10 wt.% to about 30 wt. %, from about 15 wt. % to about 50 wt. %, from about15 wt. % to about 40 wt. %, from about 15 wt. % to about 35 wt. %, fromabout 15 wt. % to about 20 wt. % (e.g., 17 wt. %), from about 25 wt. %to about 40 wt. %, or from about 30 wt. % to about 40 wt. % (e.g., 30wt. %). The carbonized binder content of the shaped porous carbonproduct is calculated by the following equation:

$\left\lbrack {1 - \frac{\left( \begin{matrix}{{Weight}\mspace{14mu} {of}\mspace{14mu} {carbonaceous}\mspace{14mu} {material}\mspace{14mu} {used}} \\{{to}\mspace{14mu} {prepare}\mspace{14mu} {shaped}\mspace{14mu} {porous}\mspace{14mu} {carbon}\mspace{14mu} {product}}\end{matrix}\mspace{14mu} \right)}{\left( {{Dry}\mspace{14mu} {weight}\mspace{14mu} {of}\mspace{14mu} {shaped}\mspace{14mu} {porous}\mspace{14mu} {carbon}\mspace{14mu} {product}} \right)}} \right\rbrack \times 100\%$

The specific surface area (BET surface area), mean pore diameter, andspecific pore volume of the shaped porous carbon products are generallycomparable to that exhibited by the carbonaceous material (e.g., carbonblack) used to prepare the products. However, the preparation processcan lead to a reduction or an increase in these characteristics of theproducts as compared to the carbonaceous material (e.g., about a 10-50%or 10-30% decrease or increase). The properties of the shaped porouscarbon products, such as specific surface area and mean pore diametercan be adjusted by selection of the type of carbonaceous material (e.g.,carbon black), the type of binder, the concentration of the binder, theamount of solvent (e.g., water) in the carbon-binder mixture, amongother parameters. For example, to obtain a shaped porous carbon producthaving a specific surface area in the range of about 50 m²/g to about100 m²/g, then a carbon black having a specific surface within or aroundthis range can be selected (e.g., ENSACO 150G, ENSACO 250G, ENSACO 250Pfrom Imerys Graphite & Carbon (TIMCAL) or N115 from Sid Richardson).

Further, selection of the binder can influence these properties as well.To determine the potential effects of a particular binder on theproperties of the shaped porous carbon product, the binder can becarbonized alone (e.g., without the carbon black) and then analyzed forthe properties of interest. For example, carbonization of a glucosebinder can result in a porous material having a broad pore sizedistribution with a BET specific surface area of approximately 150 m²/g.Thus, selection of a carbon black material such as ENSACO 150G and aglucose binder can result in a shaped porous carbon product having a BETspecific surface area greater than that measured for the carbon blackmaterial itself

In various embodiments (e.g., when the carbonaceous material comprisesor consists essentially of carbon black), the shaped porous carbonproduct has a specific surface area have a BET specific surface areathat is at least about 5 m²/g, at least about 7 m²/g, or at least about10 m²/g. For example, the BET specific surface can be in the range offrom about 5 m²/g to about 500 m²/g, from about 5 m²/g to about 350m²/g, from about 5 m²/g to about 250 m²/g, from about 5 m²/g to about225 m²/g, from about 5 m²/g to about 200 m²/g, from about 5 m²/g toabout 175 m²/g, from about 5 m²/g to about 150 m²/g, from about 5 m²/gto about 125 m²/g, from about 5 m²/g to about 100 m²/g, from about 7m²/g to about 500 m²/g, from about 7 m²/g to about 350 m²/g, from about7 m²/g to about 250 m²/g, from about 7 m²/g to about 225 m²/g, fromabout 7 m²/g to about 200 m²/g, from about 7 m²/g to about 175 m²/g,from about 7 m²/g to about 150 m²/g, from about 7 m²/g to about 125m²/g, from about 7 m²/g to about 100 m²/g, from about 10 m²/g to about500 m²/g, from about 10 m²/g to about 350 m²/g, from about 10 m²/g toabout 250 m²/g, from about 10 m²/g to about 225 m²/g, from about 10 m²/gto about 200 m²/g, from about 10 m²/g to about 175 m²/g, from about 10m²/g to about 150 m²/g, from about 10 m²/g to about 125 m²/g, or fromabout 10 m²/g to about 100 m²/g. In various embodiments, the BETspecific surface area of the shaped porous carbon black product is inthe range of from about 20 m²/g to about 500 m²/g from about 20 m²/g toabout 350 m²/g, from about 20 m²/g to about 250 m²/g, from about 20 m²/gto about 225 m²/g, from about 20 m²/g to about 200 m²/g, from about 20m²/g to about 175 m²/g, from about 20 m²/g to about 150 m²/g, from about20 m²/g to about 125 m²/g, or from about 20 m²/g to about 100 m²/g, fromabout 25 m²/g to about 500 m²/g, from about 25 m²/g to about 350 m²/g,from about 25 m²/g to about 250 m²/g, from about 25 m²/g to about 225m²/g, from about 25 m²/g to about 200 m²/g, from about 25 m²/g to about175 m²/g, from about 25 m²/g to about 150 m²/g, from about 25 m²/g toabout 125 m²/g, from about 25 m²/g to about 100 m²/g, from about 25 m²/gto about 75 m²/g, from about 30 m²/g to about 500 m²/g, from about 30m²/g to about 350 m²/g, from about 30 m²/g to about 250 m²/g, from about30 m²/g to about 225 m²/g, from about 30 m²/g to about 200 m²/g, fromabout 30 m²/g to about 175 m²/g, from about 30 m²/g to about 150 m²/g,from about 30 m²/g to about 125 m²/g, from about 30 m²/g to about 100m²/g, or from about 30 m²/g to about 70 m²/g. The BET specific surfacearea of the shaped porous carbon product is determined from nitrogenadsorption data using the Brunauer, Emmett and Teller. See the methodsdescribed in J. Am. Chem. Soc. 1938, 60, 309-331 and ASTM Test MethodsD3663, D6556 or D4567, which are Standard Test Methods for Surface AreaMeasurements by Nitrogen Adsorption.

When carbon black is the carbonaceous material, the shaped porous carbonproducts typically have a mean pore diameter greater than about 5 nm,greater than about 10 nm, greater than about 12 nm, greater than about14 nm, greater than about 20 nm, greater than about 30 nm, and oftengreater than about 40 nm. In some embodiments, the mean pore diameter ofthe shaped porous carbon product is from about 5 nm to about 100 nm,from about 5 nm to about 70 nm, from 5 nm to about 50 nm, from about 5nm to about 25 nm, from about 10 nm to about 100 nm, from about 10 nm toabout 70 nm, from 10 nm to about 50 nm, or from about 10 nm to about 25nm. In accordance with some embodiments, the mean pore diameter of theshaped porous carbon product is in the range of from about 30 nm toabout 100 nm, from about 30 nm to about 90 nm greater, from 30 nm toabout 80 nm, from 30 nm to about 70 nm, or from about 30 nm to about 60nm.

Also, when carbon black is the carbonaceous material, the shaped porouscarbon products of the present invention can have specific pore volumesof the pores having a diameter of 1.7 nm to 100 nm as measured by theBJH method that are generally greater than about 0.1 cm³/g, greater thanabout 0.2 cm³/g, or greater than about 0.3 cm³/g. In variousembodiments, the shaped porous carbon products have a specific porevolume of the pores having a diameter of 1.7 nm to 100 nm as measured bythe BJH method that is from about 0.1 cm³/g to about 1.5 cm³/g, fromabout 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g toabout 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, from about 0.2cm³/g to about 1 cm³/g, from about 0.2 cm³/g to about 0.9 cm³/g, fromabout 0.2 cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g to about 0.7cm³/g, from about 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g toabout 0.5 cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g, fromabout 0.3 cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g to about 0.6cm³/g, or from about 0.3 cm³/g to about 0.5 cm³/g. Mean pore diametersand specific pore volumes are determined in accordance with theprocedures described in E. P. Barrett, L. G. Joyner, P. P. Halenda, J.Am. Chem. Soc. 1951, 73, 373-380 (BJH method), and ASTM D4222-03(2008)Standard Test Method for Determination of Nitrogen Adsorption andDesorption Isotherms of Catalysts and Catalyst Carriers by StaticVolumetric Measurements, which are incorporated herein by reference.

It has been observed that the magnitude of the specific surface area isgenerally proportional to the concentration of micropores in the shapedporous carbon product structure. In particular, shaped porous carbonproducts prepared with carbon black generally possess a lowconcentration of pores having a diameter less than 1.7 nm. Typically,pores having a diameter less than 1.7 nm constitute no more than about10%, no more than about 5%, no more than about 4%, no more than about3%, or no more than about 2.5% of the pore volume of the shaped porouscarbon product. Similarly, in various embodiments, the pore sizedistribution of the shaped porous carbon products prepared with carbonblack is such that peaks below about 10 nm or about 5 nm are notobserved. For example, the shaped porous carbon products can have a poresize distribution such that the peak of the distribution is at adiameter greater than about 5 nm, greater than about 7.5 nm, greaterthan about 10 nm, greater than about 12.5 nm, greater than about 15 nm,or greater than about 20 nm. Also, the shaped porous carbon product canhave a pore size distribution such that the peak of the distribution isat a diameter less than about 100 nm, less than about 90 nm, less thanabout 80 nm, or less than about 70 nm.

Moreover, shaped porous carbon product prepared with carbon blackadvantageously exhibits a high concentration of mesopores between about10 nm to about 100 nm or between about 10 nm to about 50 nm.Accordingly, in various embodiments, at least about 50%, at least about60%, at least about 70%, at least about 80%, or at least about 90% ofthe pore volume of the shaped porous carbon product, as measured by theBJH method on the basis of pores having a diameter from 1.7 nm to 100nm, is attributable to pores having a pore diameter in the range of fromabout 10 nm to about 100 nm. For example, from about 50% to about 95%,from about 50% to about 90%, from about 50% to about 80%, from about 60%to about 95%, from about 60% to about 90%, from about 60% to about 80%,from about 70% to about 95%, from about 70% to about 90%, from about 70%to about 80%, from about 80% to about 95%, or from about 80% to about90% of the pore volume of the shaped porous carbon product, as measuredby the BJH method on the basis of pores having a diameter from 1.7 nm to100 nm, is attributable to pores having a pore diameter in the range offrom about 10 nm to about 100 nm. Also, in various embodiments, at leastabout 35%, at least about 40%, at least about 45%, or at least about 50%of the pore volume of the shaped porous carbon product, as measured bythe BJH method on the basis of pores having a diameter from 1.7 nm to100 nm, is attributable to pores having a pore diameter in the range offrom about 10 nm to about 50 nm. For example, from about 35% to about80%, from about 35% to about 75%, from about 35% to about 65%, fromabout 40% to about 80%, from about 40% to about 75%, or from about 40%to about 70% of the pore volume of the shaped porous carbon product, asmeasured by the BJH method on the basis of pores having a diameter from1.7 nm to 100 nm, is attributable to pores having a pore diameter in therange of from about 10 nm to about 50 nm.

Typically, the shaped porous carbon product prepared with carbon blackexhibits a relatively low concentration of pores less having a diameterthat is less than 10 nm, less than 5 nm, or less than 3 nm. For example,no more than about 10%, no more than about 5%, or no more than about 1%of the pore volume of the shaped porous carbon product, as measured bythe BJH method on the basis of pores having a diameter from 1.7 nm to100 nm, is attributable to pores having a pore diameter less than 10 nm,less than 5 nm, or less than 3 nm. In various embodiments, from about0.1% to about 10%, from about 0.1% to about 5%, from about 0.1% to about1%, from about 1% to about 10%, or from about 1% to about 5% of the porevolume of the shaped porous carbon product, as measured by the BJHmethod on the basis of pores having a diameter from 1.7 nm to 100 nm, isattributable to pores having a pore diameter less than 10 nm, less than5 nm, or less than 3 nm.

The shaped porous carbon products described herein are mechanicallystrong and stable. Crush strength represents the resistance of a solidto compression, and is an important property in the industrial use ofthe shaped porous carbon product as described herein. Instruments formeasuring the piece crush strength of individual solid particlesgenerally include a dynamometer that measures the force progressivelyapplied to the solid during the advancement of a piston. The appliedforce increases until the solid breaks and collapses into small piecesand eventually powder. The corresponding value of the collapsing forceis defined as piece crush strength and is typically averaged overmultiple samples. Standard protocols for measuring crush strength areknown in the art. For example, the mechanical strength of the shapedporous carbon product can be measured by piece crush strength testprotocols described by ASTM D4179 or ASTM D6175, which are incorporatedherein by reference. Some of these test methods are reportedly limitedto particles of a defined dimensional range, geometry, or method ofmanufacture. However, crush strength of irregularly shaped particles andparticles of varying dimension and manufacture may nevertheless beadequately measured by these and similar test methods.

In various embodiments, the shaped porous carbon product prepared inaccordance with the present invention has a radial piece crush strengthof greater than about 4.4 N/mm (1 lb/mm), greater than about 8.8 N/mm (2lbs/mm), greater than about 13.3 N/mm (3 lbs/mm), greater than about17.6 N/mm (4 lbs/mm), or greater than about 20 N/mm (4.5 lbs/mm). Incertain embodiments, the radial piece crush strength of the shapedporous carbon product is from about 4.4 N/mm (1 lb/mm) to about 88 N/mm(20 lbs/mm), from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15 lbs/mm),from about 8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm), from about15 N/mm (3.4 lbs/mm) to about 88 N/mm (20 lbs/mm), from about 15 N/mm(3.4 lbs/mm) to about 44 N/mm (10 lbs/mm), from about 17 N/mm (3.8lbs/mm) to about 88 N/mm (20 lbs/mm), from about 17 N/mm (3.8 lbs/mm) toabout 44 N/mm (10 lbs/mm), from about 20 N/mm (4.5 lbs/mm) to about 88N/mm (20 lbs/mm), or from about 20 N/mm (4.5 lbs/mm) to about 44 N/mm(10 lbs/mm). In radial piece crush strength measurements, the measuredforce is relative to the dimension of the solid perpendicular to theapplied load, which typically can range from about 0.5 mm to about 20mm, from about 1 mm to about 10 mm, or from about 1.5 mm to 5 mm. Forirregularly shaped porous carbon products, the radial piece crushstrength is measured by applying the load perpendicular to the longestdimension of the solid.

Mechanical piece crush strength can also be reported on a basis that isunitless with respect to the dimension of the shaped porous carbonproduct (e.g., for generally spherically shaped solids or solids havingapproximately equal transverse dimensions). The shaped porous carbonproduct prepared in accordance with the present invention typically hasa piece crush strength greater than about 22 N (5 lbs), greater thanabout 36 N (8 lbs), or greater than about 44 N (10 lbs). In variousembodiments, shaped porous carbon product may have a piece crushstrength from about 22 N (5 lbs) to about 88 N (20 lbs), from about 22 N(5 lbs) to about 66 N (15 lbs), or from about 33 N (7.5 lbs) to about 66N (15 lbs).

In addition to crush strength, the shaped porous carbon products alsoexhibit desirable attrition and abrasion resistance characteristics.There are several test methods suitable for determining the attritionand abrasion resistance of the shaped porous carbon products andcatalysts produced in accordance with the present disclosure. Thesemethods are a measure of the propensity of the material to produce finesin the course of transportation, handling, and use on stream.

One such method is the attrition index as determined in accordance withASTM D4058-96 (Standard Test Method for Attrition and Abrasion ofCatalysts and Catalyst Carriers), which is a measurement of theresistance of a material (e.g., extrudate or catalyst particle) toattrition wear due to the repeated striking of the particle against hardsurfaces within a specified rotating test drum and is incorporatedherein by reference. This test method is generally applicable totablets, extrudates, spheres, granules, pellets as well as irregularlyshaped particles typically having at least one dimension larger thanabout 1.6 mm ( 1/16 inch) and smaller than about 19 mm (¾ inch),although attrition measurements can also be performed on larger sizematerials. Variable and constant rate rotating cylinder abrasimetersdesigned according to ASTM D4058-96 are readily available. Typically,the material to be tested is placed in drum of the rotating testcylinder and rolled at from about 55 to about 65 RPM for about 35minutes. Afterwards, the material is removed from test cylinder andscreened on a 20-mesh sieve. The percentage (by weight) of the originalmaterial sample that remains on the 20-mesh sieve is referred to as the“percent retained.” The shaped porous carbon products (e.g., extrudates)and catalysts prepared therefrom typically exhibit a rotating drumattrition index as measured in accordance with ASTM D4058-96 or similartest method such that the percent retained is greater than about 85%,greater than about 90%, greater than about 92%, greater than about 95%,greater than about 97%, or greater than about 99% by weight. A percentretained result of greater than about 97% is indicative of materialswith exceptional mechanical stability and robust structure particularlydesirable for industrial applications.

Abrasion loss (ABL) is an alternate measurement of the resistance of theshaped porous carbon products (e.g., extrudates) and catalysts preparedtherefrom. As with the attrition index, the results of this test methodcan be used as a measure of fines production during the handling,transportation, and use of the material. Abrasion loss is a measurementof the resistance of a material to attrition wear due to the intensehorizontal agitation of the particles within the confines of a 30-meshsieve. Typically, the material to be tested is first de-dusted on a20-mesh sieve by gently moving the sieve side-to-side at least about 20times. The de-dusted sample is weighed and then transferred to theinside of a clean, 30-mesh sieve stacked above a clean sieve pan for thecollection of fines. The complete sieve stack is then assembled onto asieve shaker (e.g., RO-Tap RX-29 sieve shaker from W.S. Tyler IndustrialGroup, Mentor, Ohio), covered securely and shaken for about 30 minutes.The collected fines generated are weighed and divided by the de-dustedsample weight to provide a sample abrasion loss in percent by weight.The shaped porous carbon products (e.g., extrudates) and catalystsprepared therefrom typically exhibit a horizontal agitation sieveabrasion loss of less than about 5%, less than about 3%, less than about2%, less than about 1%, less than about 0.5%, less than about 0.2%, lessthan about 0.1%, less than about 0.05%, or less than about 0.03% byweight. An abrasion loss result of less than about 2% is particularlydesired for industrial applications.

As previously noted herein, the shaped porous carbon products of thepresent invention can exhibit a high wettability, which improvescatalyst preparation when these products are used as catalyst supports.Applicants have discovered that wettability of the shaped porousproducts can be enhanced by employing certain pyrolysis (carbonization)conditions as described herein. As used herein, the term “wettability”refers to the rate at which the shaped porous product takes up water.Wettability can be measured using techniques known in the art. Forinstance, in the context of preparing a catalyst using the shaped porouscarbon product as a support, a measurement of the time needed forincipient wetness impregnation can provide a direct indication of thewetting rate of the product. The time needed for incipient wetnessimpregnation is measured starting at the time when the liquid containingthe catalyst active component or precursor thereof is contacted with thecatalyst support (i.e., shaped porous carbon product) and ending at thetime when no remaining liquid is visible (i.e., when the liquid has beenfully absorbed by the support).

In particular, it has been discovered that wettability can be improvedby pyrolyzing the shaped carbon composite (i.e., carbonizing the binder)in a heating zone that is maintained at an elevated temperature (e.g.,greater than about 400° C. and higher carbonization temperatures withinthe ranges specified herein) or that includes a series of heating stages(multi-staged) that are each maintained at an elevated temperature(e.g., greater than about 400° C. and higher carbonization temperatureswithin the ranges specified herein). Shaped porous carbon productspyrolyzed under these temperature conditions exhibit improvedwettability as compared to a control product (shaped porous carbonproduct control 1) that is prepared by an otherwise identical process,but is pyrolyzed in a heating zone where upon introducing the shapedcarbon composite to the heating zone, the temperature of the heatingzone is ramped from ambient temperature or relatively low temperature(e.g., less than about 100° C.) to the elevated temperature (e.g., about800° C.). Specifically, the shaped porous carbon product control 1 isprepared by the process described in Example 17 in which the shapedcarbon composite (e.g., carbon black extrudate) is heated in a heatingzone (e.g., continuous rotary tube furnace) in which the temperature isramped from ambient to 800° C. under nitrogen atmosphere.

One shaped porous carbon product having improved wettability over theshaped carbon porous control product 1 can be prepared according to theprocess described in

Example 18 in which the shaped carbon composite was pyrolyzed to formthe shaped porous carbon product in a continuous rotary kiln maintainedat a temperature between approximately 760° C. to 820° C. under nitrogenatmosphere. As such, in some embodiments where a single temperatureheating zone (e.g., continuous rotary kiln) is used, the temperature canrange from about 750° C. to about 850° C. and the residence time canrange from about 30 to about 90 minutes. Alternatively, a shaped porouscarbon product having improved wettability over the shaped porous carbonproduct control 1 can be prepared by a process that includes pyrolyzingthe shaped carbon composite in a heating zone that comprises at leasttwo heating stages.

In accordance with these aspects of the present invention, one highlywettable shaped porous carbon product comprises carbon black and acarbonized binder comprising a carbonization product of an organicbinder, wherein the shaped porous carbon product has a BET specificsurface area from about 25 m²/g to about 500 m²/g, a mean pore diametergreater than about 10 nm, a specific pore volume greater than about 0.1cm³/g, a radial piece crush strength greater than about 4.4 N/mm (1lb/mm), greater than about 8.8 N/mm (2 lbs/mm), greater than about 13.3N/mm (3 lbs/mm), greater than about 15 N/mm (3.4 lbs/mm), greater thanabout 17 N/mm (3.8 lbs/mm), or greater than about 20 N/mm (4.5 lbs/mm),and a carbon black content of at least about 35 wt. %, and wherein theshaped porous carbon product has improved wettability over shaped porouscarbon product control 1 (prepared according to Example 17).

Another highly wettable shaped porous carbon product of the presentinvention comprises a carbon agglomerate comprising the carbonaceousmaterial wherein the shaped porous carbon product has a diameter of atleast about 50 μm, a BET specific surface area from about 25 m²/g toabout 500 m²/g, a mean pore diameter greater than about 10 nm, aspecific pore volume greater than about 0.1 cm³/g, and a radial piececrush strength greater than about 4.4 N/mm (1 lb/mm), greater than about8.8 N/mm (2 lbs/mm), greater than about 13.3 N/mm (3 lbs/mm), greaterthan about 15 N/mm (3.4 lbs/mm), greater than about 17 N/mm (3.8lbs/mm), or greater than about 20 N/mm (4.5 lbs/mm), and wherein theshaped porous carbon product has improved wettability over shaped porouscarbon product control 1 (prepared according to Example 17).

The shaped porous carbon products and methods for preparing the shapedporous carbon products of the present invention include variouscombinations of features described herein. For example, in variousembodiments, the shaped porous carbon product comprises (a) carbon blackand (b) a carbonized binder comprising a carbonization product of awater soluble organic binder, wherein the shaped porous carbon producthas a BET specific surface area from about 20 m²/g to about 500 m²/g orfrom about 25 m²/g to about 250 m²/g, a mean pore diameter greater thanabout 10 nm, a specific pore volume greater than about 0.1 cm³/g, aradial piece crush strength greater than about 4.4 N/mm (1 lb/mm), and acarbon black content of at least about 35 wt. %. In other embodiments,the shaped porous carbon product comprises a carbon agglomerate, whereinthe shaped porous carbon product has a diameter of at least about 50 μm,a BET specific surface area from about 20 m²/g to about 500 m²/g or fromabout 25 m²/g to about 250 m²/g, a mean pore diameter greater than about10 nm, a specific pore volume greater than about 0.1 cm³/g, and a radialpiece crush strength greater than about 4.4 N/mm (1 lb/mm).

The shaped porous carbon product of the present invention may also havea low sulfur content. For example, the sulfur content of the shapedporous carbon product may be no greater than about 1 wt. % or no greaterthan about 0.1 wt. %.

Features and characteristics including the type of carbonaceous material(e.g., carbon black), the binder, the specific surface area, thespecific pore volume, the mean pore diameter, the crush strength,attrition and abrasion resistance and the carbon black content may beindependently adjusted or modified within the ranges described herein.Also, shaped porous carbon products may be further defined according tocharacteristics described herein.

For instance, the shaped porous carbon product can comprises (a) carbonblack and (b) a carbonized binder comprising a carbonization product ofa water soluble organic binder and wherein the shaped porous carbonproduct has a BET specific surface area from about 20 m²/g to about 500m²/g, a mean pore diameter greater than about 5 nm, a specific porevolume greater than about 0.1 cm³/g, a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), a carbon black content of atleast about 35 wt. %, and a carbonized binder content from about 5 wt. %to about 65 wt. % (e.g., from about 20 wt. % to about 50 wt. %).

In other embodiments, a shaped porous carbon product of the presentinvention comprises (a) carbon black and (b) a carbonized bindercomprising a carbonization product of a water soluble organic binder,wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250m²/g, a mean pore diameter greater than about 10 nm, a specific porevolume greater than about 0.1 cm³/g, a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), and a carbon black content of atleast about 35 wt. %, and wherein the shaped porous carbon product has apore volume measured on the basis of pores having a diameter from 1.7 nmto 100 nm and at least about 35% of the pore volume is attributable topores having a pore diameter in the range of from about 10 nm to about50 nm.

Yet another shaped porous carbon product of the present inventioncomprises a carbon agglomerate, wherein the shaped porous carbon producthas a diameter of at least about 50 μm, a BET specific surface area fromabout 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250 m²/g,a mean pore diameter greater than about 10 nm, a specific pore volumegreater than about 0.1 cm³/g, and a radial piece crush strength greaterthan about 4.4 N/mm (1 lb/mm), and wherein the shaped porous carbonproduct has a pore volume measured on the basis of pores having adiameter from 1.7 nm to 100 nm and at least about 35% of the pore volumeis attributable to pores having a pore diameter in the range of fromabout 10 nm to about 50 nm.

One specific series of the shaped porous carbon products which areparticularly useful as catalyst supports comprise (a) carbon black and(b) a carbonized binder comprising a carbonization product of a watersoluble organic binder, wherein the shaped porous carbon product has aBET specific surface area from about 25 m²/g to about 100 m²/g or fromabout 30 m²/g to about 75 m²/g, a mean pore diameter greater than about30 nm (e.g., from about 30 nm to about 75 nm), and a radial piece crushstrength greater than about 8.8 N/mm (2 lb/mm). Shaped porous carbonproducts suitable for use as catalyst supports include those whichcomprise a carbon agglomerate, wherein the shaped porous carbon producthas a diameter of at least about 50 μm, BET specific surface area fromabout 25 m²/g to about 100 m²/g or from about 30 m²/g to about 75 m²/g,a mean pore diameter greater than about 30 nm (e.g., in the range offrom about 30 nm to about 75 nm), and a radial piece crush strengthgreater than about 8.8 N/mm (2 lb/mm). The carbon black content of theseshaped porous carbon products is typically at least about 50 wt. %, atleast about 60 wt. %, at least about 70 wt. %, or at least about 80 wt.%.

Methods of the present invention include various combinations of thefeatures, characteristics, and method steps described herein. Forexample, various methods for preparing the shaped porous carbon productinclude mixing and heating water and a water soluble organic binder toform a binder solution, wherein the water and binder are heated to atemperature of at least about 50° C., and wherein the binder comprises:(i) a saccharide selected from the group consisting of a monosaccharide,a disaccharide, an oligosaccharide, a derivative thereof, and anycombination thereof and (ii) a polymeric carbohydrate, a derivative of apolymeric carbohydrate, or a non-carbohydrate synthetic polymer, or anycombination thereof; mixing carbon black particles with the bindersolution to produce a carbon black mixture; forming the carbon blackmixture to produce a shaped carbon black composite; and heating theshaped carbon black composite to carbonize the binder to a waterinsoluble state and to produce a shaped porous carbon product.

Other methods for preparing the shaped porous carbon product includemixing water, carbon black, and a water soluble organic binder to form acarbon black mixture, wherein the binder comprises: (i) a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, and any combination thereofand (ii) a polymeric carbohydrate, a derivative of a polymericcarbohydrate, or a non-carbohydrate synthetic polymer, or anycombination thereof; forming the carbon black mixture to produce ashaped carbon black composite; and heating the shaped carbon blackcomposite to carbonize the binder to a water insoluble state and toproduce a shaped porous carbon product.

Further methods include mixing water, carbon black, and a binder to forma carbon black mixture, wherein the binder comprises a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, or any combination thereof andwherein the weight ratio of the binder to carbon black in the carbonblack mixture is at least about 1:4, at least about 1:3, at least about1:2, at least about 1:1, or at least 1.5:1; forming the carbon blackmixture to produce a shaped carbon black composite; and heating theshaped carbon black composite to carbonize the binder to a waterinsoluble state and to produce a shaped porous carbon product.

Still other methods include mixing water, carbon black, and a binder toform a carbon black mixture, wherein the binder comprises a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, or any combination thereof andwherein the water content of the carbon black mixture is no more thanabout 80% by weight, no more than about 55% by weight, no more thanabout 40% by weight, or no more than about 25% by weight; forming thecarbon black mixture to produce a shaped carbon black composite; andheating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce a shaped porous carbon product.

Another method of preparing the shaped porous carbon product byextrusion preferably comprises mixing carbon black particles with anaqueous solution comprising a water soluble organic binder compoundselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a polysaccharide, and combinations thereof toproduce a carbon black mixture, wherein the carbon black mixturecomprises at least about 40 wt. % of the carbon black and at least about40 wt. % of the binder on a dry basis; forming the carbon black mixtureunder a pressure of at least 500 kPa (5 bar) to produce a shaped carbonblack composite; drying the shaped carbon black material at atemperature in the range of from about room temperature (e.g., about 20°C.) to about 150° C.; and heating the dried shaped carbon blackcomposite to a temperature between about 250° C. and about 800° C. in anoxidative, inert, or reductive atmosphere (e.g., an inert N₂ atmosphere)to carbonize the binder to a water insoluble state and produce theshaped porous carbon product, wherein the shaped porous carbon producthas a diameter of at least about 50 μm, a BET specific surface area fromabout 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250 m²/g,a mean pore diameter greater than about 10 nm, a specific pore volumegreater than about 0.1 cm³/g, and a radial piece crush strength greaterthan about 4.4 N/mm (1 lb/mm). Typically, the water soluble organicbinder compound is selected from the group consisting of amonosaccharide, an oligosaccharide, a polysaccharide, and combinationsthereof. The carbon black content of the shape porous carbon product canbe at least about 35 wt. % or as described herein. Also, in someembodiments, the shaped porous carbon product has a pore volume measuredon the basis of pores having a diameter from 1.7 nm to 100 nm and atleast about 35% of the pore volume is attributable to pores having apore diameter in the range of from about 10 nm to about 50 nm. Thecarbon black mixture may optionally be heated during the forming step(e.g., extrusion, pelletizing, pilling, tableting, cold or hot isostaticpressing, calandering, injection molding, 3D printing, drip casting, orother methods) to facilitate the forming of the carbon black mixtureinto the desired shape.

Additional shaped porous carbon products and methods of preparation ofthe present invention include any combinations of the features describedherein and where features described above are independently substitutedor added to the aforementioned embodiments.

The shaped porous carbon products can also be wash-coated or dip-coatedonto other materials to prepare structured composite materials. Theshaped porous carbon products (at least micron-sized) can be domains onheterogeneous, segregated composite materials (e.g., carbon—ZrO₂composites or carbon domains hosted by large-pore (mm-sized) ceramicfoams) as well as layered or structured materials (e.g., carbon blackwash-coats onto inert supports such as steatite, plastic or glassballs).

The shaped porous carbon product of the invention may be further treatedthermally or chemically to alter the physical and chemicalcharacteristics of the shaped porous carbon product. For examplechemical treatment such as an oxidation may a produce a more hydrophilicsurface which may provide advantages for preparing a catalyst (improvedwetting and dispersion). Oxidation methods are known in the art, see forexample U.S. Pat. Nos. 7,922,805 and 6,471,763. In other embodiments,the shaped porous carbon product has been surface treated using knownmethods for attaching a functional group to a carbon based substrate.See, e.g., WO2002/018929, WO97/47691, WO99/23174, WO99/31175,WO99/51690, WO2000/022051, and WO99/63007, all of which are incorporatedherein by reference. The functional group may be an ionizable group suchthat when the shaped porous carbon product is subjected to ionizingconditions, it comprises an anionic or cationic moiety. This embodimentis useful when the shaped porous carbon product is used as a separationmedia in chromatography columns and other separation devices.

Catalyst Compositions and Methods of Preparation

Various aspects of the present invention are also directed to catalystcompositions comprising the shaped porous carbon product as a catalystsupport and methods of preparing the catalyst compositions. The shapedporous carbon products of the present invention provide effectivedispersion and anchoring of catalytically active components orprecursors thereof to the surface of the carbon product. The catalystcompositions of the present invention are suitable for use in long termcontinuous flow operation phase reactions under demanding reactionconditions such as liquid phase reactions in which the shaped porouscarbon product is exposed to reactive solvents such as acids and waterat elevated temperatures. The catalyst compositions comprising theshaped porous carbon products of the present invention demonstrateoperational stability necessary for commodity applications.

In general, the catalyst compositions of the present invention comprisethe shaped porous carbon product as a catalyst support and acatalytically active component or precursor thereof at a surface of thesupport (external and/or internal surface). In various catalystcompositions of the present invention, the catalytically activecomponent or precursor thereof comprises a metal at a surface of theshaped porous carbon product. In these and other embodiments, the metalcomprises at least one metal selected from groups IV, V, VI, VII, VIII,IX, X, XI, XII, and XIII. Some preferred metals include cobalt, nickel,copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium,rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold,and combinations thereof. In various embodiments, the metal comprises atleast one d-block metal. Some preferred d-block metals are selected fromthe group consisting of cobalt, nickel, copper, zinc, iron, ruthenium,rhodium, palladium, silver, osmium, iridium, platinum, gold andcombinations thereof. Typically, the metal(s) at a surface of thecatalyst support may constitute from about 0.1% to about 50%, from about0.1% to about 25%, from about 0.1% to about 10%, from about 0.1% toabout 5%, from about 0.25% to about 50%, from about 0.25% to about 25%,from about 0.25% to about 10%, from about 0.25% to about 5%, from about1% to about 50%, from about 1% to about 25%, from about 1% to about 10%,from about 1% to about 5%, from about 5% to about 50%, from about 5% toabout 25%, or from about 5% to about 10% of the total weight of thecatalyst.

In general, the metals may be present in various forms (e.g., elemental,metal oxide, metal hydroxides, metal ions, metalates, polyanions,oligomers or colloidal etc.). Typically, however, the metals are reducedto elemental form during preparation of the catalyst composition orin-situ in the reactor under reaction conditions.

The metal(s) may be deposited on a surface of the shaped porous carbonproduct according to procedures known in the art including, but notlimited to incipient wetness, ion-exchange, deposition-precipitation,coating and vacuum impregnation. When two or more metals are depositedon the same support, they may be deposited sequentially orsimultaneously. Multiple impregnation steps are also possible (e.g.,dual impregnation of the same metal under different conditions toincrease overall metal loading or tune the metal distribution across theshell). In various embodiments, the metal(s) deposited on the shapedporous carbon product for the oxidation catalyst form a shell at leastpartially covering the surface of the carbon product. In other words,metal deposited on the shaped porous carbon product coats externalsurfaces of the carbon product. In various embodiments, the metalpenetrates surficial pores of the shaped porous carbon product to form ashell layer (“egg shell”) with a thickness of from about 10 μm to about400 μm, or from about 50 μm to about 150 μm (e.g., about 100 μm). Incertain embodiments the shell may be produced sub-surface to produce a10 μm to about 400 μm sub-surface band containing the catalyticallyactive metals (“egg yolk”). Also structured shells featuring differentmetal distributions across the shell for the various metals arepossible.

In other embodiments, the metal(s) may be deposited on the carbonaceousmaterials (e.g., carbon black particles) before forming the shapedporous carbon product. Accordingly, in these embodiments, thecarbon-binder mixture (e.g., carbon black mixture) may further comprisea metal, such as, for example, a d-block metal. Some preferred d-blockmetals are selected from the group consisting of cobalt, nickel, copper,zinc, iron, ruthenium, rhodium, palladium, silver, osmium, iridium,platinum, gold and combinations thereof. In various embodiments, themetal comprises at least one metal selected from groups IV, V, VI, VII,VIII, IX, X, XI, XII, and XIII. Preferred metals include cobalt, nickel,copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium,rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold,and combinations thereof. Typically, the metal(s) may constitute fromabout 0.1% to about 50%, from about 0.1% to about 25%, from about 0.1%to about 10%, from about 0.1% to about 5%, from about 0.25% to about50%, from about 0.25% to about 25%, from about 0.25% to about 10%, fromabout 0.25% to about 5%, from about 1% to about 50%, from about 1% toabout 25%, from about 1% to about 10%, from about 1% to about 5%, fromabout 5% to about 50%, from about 5% to about 25%, or from about 5% toabout 10%. For example, when the metal used is a noble metal, the metalcontent can be from about 0.25% to about 10% of the total weight of theshaped porous carbon product. Alternatively, when the metal used is anon-noble metal, the metal content can be from about 0.1% to about 50%of the total weight of the shaped porous carbon product.

In various embodiments, following metal deposition, the catalystcomposition is optionally dried, for example, at a temperature of atleast about 50° C., more typically at least about 120° C. for a periodof time of at least about 1 hour, more typically 3 hours or more.Alternatively, the drying may be conducted in a continuous or stagedmanner where independently controlled temperature zones (e.g., 60° C.,80° C., and 120° C.) are utilized. Typically, drying is initiated belowthe boiling point of the solvent, e.g., 60° C. and then increased. Inthese and other embodiments, the catalyst is dried under sub-atmosphericor atmospheric pressure conditions. In various embodiments, the catalystis reduced after drying (e.g., by flowing 5% H₂ in N₂ at 350° C. for 3hours). Still further, in these and other embodiments, the catalyst iscalcined, for example, at a temperature of at least about 200° C. for aperiod of time (e.g., at least about 3 hours).

In some embodiments, the catalyst composition of the present inventionis prepared by depositing the catalytically active component orprecursor thereof subsequent to forming the shaped porous carbon product(i.e., depositing directly on a surface of the shaped porous carbonproduct). The catalyst composition of the present invention can beprepared by contacting the shaped porous carbon product with asolubilized metal complex or combination of solubilized metal complexes.The heterogeneous mixture of solid and liquids can then be stirred,mixed and/or shaken to enhance the uniformity of dispersion of thecatalyst, which, in turn, enables the more uniform deposition ofmetal(s) on the surface of the support upon removal of the liquids.Following deposition, the metal complex(es) on the shaped porous carbonproducts are heated and reduced under a reducing agent such as ahydrogen containing gas (e.g., forming gas 5% H₂ and 95% N₂). Thetemperature at which the heating is conducted generally ranges fromabout 150° C. to about 600° C., from about 200° C. to about 500° C., orfrom about 100° C. to about 400° C. Heating is typically conducted for aperiod of time ranging from about 1 hour to about 5 hours or from about2 hour to about 4 hours. Reduction may also be carried in the liquidphase. For example, catalyst compositions can be treated in a fixed bedwith the liquid containing a reducing agent pumped through the staticcatalyst.

In other embodiments, the catalyst composition of the present inventionis prepared by depositing the catalytically active component orprecursor thereof on the carbonaceous material (e.g., carbon black)prior to forming the shaped porous carbon product. In one such method, aslurry of the carbonaceous material with solubilized metal complex(es)is prepared. Carbonaceous material may be initially dispersed in aliquid such as water. Thereafter, the solubilized metal complex(es) maybe added to the slurry containing the carbonaceous material. Theheterogeneous mixture of solid and liquids can then be stirred, mixedand/or shaken to enhance the uniformity of dispersion of the catalyst,which, in turn, enables the more uniform deposition of metal(s) on thesurface of the carbonaceous material upon removal of the liquids.Following deposition, the metal complex(es) on the carbonaceous materialis heated and reduced with a reducing agent as described above. Themetal-loaded carbonaceous particles can then be formed according to themethod described for the shaped porous carbon product. The slurry canalso be wash-coated onto inert supports rather than shaped into bulkcatalyst pellets.

The catalyst compositions comprising the shaped porous carbon product asa catalyst support can be deployed in various reactor formats,particularly those suited liquid phase medium such as batch slurry,continuous slurry-based stirred tank reactors, cascade of stirred tankreactors, bubble slurry reactor, fixed beds, ebulated beds and otherknown industrial reactor formats. Accordingly, in various aspects, thepresent invention is further directed to methods of preparing a reactorvessel for a liquid phase catalytic reaction. In other aspects, thepresent invention is further directed to methods of preparing a reactorvessel for a gaseous phase catalytic reaction. The method comprisescharging the reactor vessel with a catalyst composition comprising theshaped porous carbon product as described herein as a catalyst support.In some embodiments, the reactor vessel is a fixed bed reactor.

Various methods for preparing a catalyst composition in accordance withthe present invention include mixing and heating water and a watersoluble organic binder to form a binder solution, wherein the water andbinder are heated to a temperature of at least about 50° C., and whereinthe binder comprises: (i) a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof and (ii) a polymericcarbohydrate, a derivative of a polymeric carbohydrate, or anon-carbohydrate synthetic polymer, or any combination thereof; mixingcarbon black particles with the binder solution to produce a carbonblack mixture; forming the carbon black mixture to produce a shapedcarbon black composite; heating the shaped carbon black composite tocarbonize the binder to a water insoluble state and to produce a shapedporous carbon product; and depositing a catalytically active componentor precursor thereof on the shaped porous carbon product to produce thecatalyst composition.

Other methods include mixing water, carbon black, and a water solubleorganic binder to form a carbon black mixture, wherein the bindercomprises: (i) a saccharide selected from the group consisting of amonosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and (ii) a polymeric carbohydrate,a derivative of a polymeric carbohydrate, or a non-carbohydratesynthetic polymer, or any combination thereof; forming the carbon blackmixture to produce a shaped carbon black composite; heating the shapedcarbon black composite to carbonize the binder to a water insolublestate and to produce a shaped porous carbon product; and depositing acatalytically active component or precursor thereof on the shaped porouscarbon product to produce the catalyst composition.

Further methods for preparing a catalyst composition in accordance withthe present invention include mixing water, carbon black, and a binderto form a carbon black mixture, wherein the binder comprises asaccharide selected from the group consisting of a monosaccharide, adisaccharide, an oligosaccharide, a derivative thereof, or anycombination thereof and wherein the weight ratio of the binder to carbonblack in the carbon black mixture is at least about 1:4, at least about1:3, at least about 1:2, at least about 1:1, or at least 1.5:1; formingthe carbon black mixture to produce a shaped carbon black composite;heating the shaped carbon black composite to carbonize the binder to awater insoluble state and to produce a shaped porous carbon product; anddepositing a catalytically active component or precursor thereof on theshaped porous carbon product to produce the catalyst composition.

Other methods include mixing water, carbon black, and a binder to form acarbon black mixture, wherein the binder comprises a saccharide selectedfrom the group consisting of a monosaccharide, a disaccharide, anoligosaccharide, a derivative thereof, or any combination thereof andwherein the water content of the carbon black mixture is no more thanabout 80% by weight, no more than about 55% by weight, no more thanabout 40% by weight, or no more than about 25% by weight; forming thecarbon black mixture to produce a shaped carbon black composite; heatingthe shaped carbon black composite to carbonize the binder to a waterinsoluble state and to produce a shaped porous carbon product; anddepositing a catalytically active component or precursor thereof on theshaped porous carbon product to produce the catalyst composition.

Still further methods include depositing a catalytically activecomponent or precursor thereof on a shaped porous carbon product toproduce the catalyst composition, wherein the shaped porous carbonproduct comprises: (a) carbon black and (b) a carbonized bindercomprising a carbonization product of a water soluble organic binder andwherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g, a mean pore diameter greater thanabout 5 nm, a specific pore volume greater than about 0.1 cm³/g, aradial piece crush strength greater than about 4.4 N/mm (1 lb/mm), acarbon black content of at least about 35 wt. %, and a carbonized bindercontent from about 5 wt. % to about 65 wt. % (e.g., from about 20 wt. %to about 50 wt. %).

Catalytic Processes

The catalyst compositions comprising the shaped porous carbon product ofthe present invention are useful for various catalytic conversionsincluding oxidations, reductions, dehydrations, hydrogenations and otherknown transformations using appropriate active metals formulations andwhich can be conducted in gaseous or liquid medium. Accordingly, infurther aspects, the present invention is directed to processes for thecatalytic conversion of a reactant.

Processes of the present invention comprise contacting a liquid mediumcomprising the reactant with a catalyst composition comprising theshaped porous carbon product as a catalyst support. In variousembodiments, the shaped porous carbon product comprises (a) carbon blackand (b) a carbonized binder comprising a carbonization product of awater soluble organic binder, wherein the shaped porous carbon producthas a BET specific surface area from about 20 m²/g to about 500 m²/g orfrom about 25 m²/g to about 250 m²/g, a mean pore diameter greater thanabout 10 nm, a specific pore volume greater than about 0.1 cm³/g, aradial piece crush strength greater than about 4.4 N/mm (1 lb/mm), and acarbon black content of at least about 35 wt. %. In other embodiments,the shaped porous carbon product comprises a carbon agglomerate, whereinthe shaped porous carbon product has a diameter of at least about 50 μm,a BET specific surface area from about 20 m²/g to about 500 m²/g or fromabout 25 m²/g to about 250 m²/g, a mean pore diameter greater than about10 nm, a specific pore volume greater than about 0.1 cm³/g, and a radialpiece crush strength greater than about 4.4 N/mm (1 lb/mm). Typically,the catalyst composition has superior mechanical strength (e.g.,mechanical piece crush strength and/or radial piece crush strength) andis stable to the continuous flow of the liquid medium and reactionconditions for at least about 500 hours or about 1,000 hours withoutsubstantial loss in catalytic productivity, selectivity, and/or yield.

In addition, it has been surprisingly discovered that the catalystcompositions comprising the shaped porous carbon product of the presentinvention are highly productive and selective catalysts for a certain ofchemical transformations such as the conversion of highly functionalizedand/or non-volatile molecules including, but not limited tobiorenewably-derived molecules and intermediates for commodityapplications.

Catalytic Oxidation

One series of chemical transformations that the catalyst compositions ofthe present invention are suited for is the selective oxidation of ahydroxyl group to a carboxyl group in a liquid or gaseous reactionmedium. For example, one series of chemical transformations that thecatalyst compositions of the present invention are especially suited foris the selective oxidation an aldose to an aldaric acid. Accordingly,catalyst compositions of the present invention as described herein canbe utilized as oxidation catalysts. Aldoses include, for example,pentoses and hexoses (i.e., C-5 and C-6 monosaccharides). Pentosesinclude ribose, arabinose, xylose, and lyxose, and hexoses includeglucose, allose, altrose, mannose, gulose, idose, galactose, and talose.Accordingly, in various embodiments, the present invention is alsodirected to a process for the selective oxidation of an aldose to analdaric acid comprising reacting the aldose with oxygen in the presenceof a catalyst composition as described herein to form the aldaric acid.Typically, the catalyst composition comprises at least platinum as acatalytically active component.

The catalyst compositions of the present invention have been found to beespecially selective for the oxidation of the glucose to glucaric acid.Accordingly, the present invention is directed to a process for theselective oxidation of glucose to glucaric acid comprising reacting thealdose with oxygen in the presence of a catalyst composition asdescribed herein to form glucaric acid. U.S. Pat. No. 8,669,397, theentire contents of which are incorporated herein by reference, disclosesvarious catalytic processes for the oxidation of glucose to glucaricacid. In general, glucose may be converted to glucaric acid in highyield by reacting glucose with oxygen (e.g., air, oxygen-enriched air,oxygen alone, or oxygen with other constituents substantially inert tothe reaction) in the presence of an oxidation catalyst according to thefollowing reaction:

The oxidation can be conducted in the absence of added base (e.g., KOH)or where the initial pH of the reaction medium and/or the pH of reactionmedium at any point in the reaction is no greater than about 7, nogreater than 7.0, no greater than about 6.5, or no greater than about 6.The initial pH of the reaction mixture is the pH of the reaction mixtureprior to contact with oxygen in the presence of an oxidation catalyst.In fact, catalytic selectivity can be maintained to attain glucaric acidyield in excess of about 30%, about 40%, about 50%, about 60% and, insome instances, attain yields in excess of 65% or higher. The absence ofadded base advantageously facilitates separation and isolation of theglucaric acid, thereby providing a process that is more amenable toindustrial application, and improves overall process economics byeliminating a reaction constituent. The “absence of added base” as usedherein means that base, if present (for example, as a constituent of afeedstock), is present in a concentration which has essentially noeffect on the efficacy of the reaction; i.e., the oxidation reaction isbeing conducted essentially free of added base. The oxidation reactioncan also be conducted in the presence of a weak carboxylic acid, such asacetic acid, in which glucose is soluble. The term “weak carboxylicacid” as used herein means any unsubstituted or substituted carboxylicacid having a pKa of at least about 3.5, more preferably at least about4.5 and, more particularly, is selected from among unsubstituted acidssuch as acetic acid, propionic acid or butyric acid, or mixturesthereof.

The oxidation reaction may be conducted under increased oxygen partialpressures and/or higher oxidation reaction mixture temperatures, whichtends to increase the yield of glucaric acid when the reaction isconducted in the absence of added base or at a pH below about 7.Typically, the partial pressure of oxygen is at least about 15 poundsper square inch absolute (psia) (104 kPa), at least about 25 psia (172kPa), at least about 40 psia (276 kPa), or at least about 60 psia (414kPa). In various embodiments, the partial pressure of oxygen is up toabout 1,000 psia (6895 kPa), more typically in the range of from about15 psia (104 kPa) to about 500 psia (3447 kPa), from about 75 psia (517kPa) to about 500 psia (3447 kPa), from about 100 psia (689 kPa) toabout 500 psia (3447 kPa), from about 150 psia (1034 kPa) to about 500psia (3447 kPa). Generally, the temperature of the oxidation reactionmixture is at least about 40° C., at least about 60° C., at least about70° C., at least about 80° C., at least about 90° C., at least about100° C., or higher. In various embodiments, the temperature of theoxidation reaction mixture is from about 40° C. to about 200° C., fromabout 60° C. to about 200° C., from about 70° C. to about 200° C., fromabout 80° C. to about 200° C., from about 80° C. to about 180° C., fromabout 80° C. to about 150° C., from about 90° C. to about 180° C., orfrom about 90° C. to about 150° C. Surprisingly, the catalystcompositions comprising the shaped porous carbon product as a catalystsupport permit glucose oxidation at elevated temperatures (e.g., fromabout 100° C. to about 160° C. or from about 125° C. to about 150° C.)without heat degradation of the catalyst. In particular, reactor formatssuch as a fixed bed reactor which can provide a relatively high liquidthroughput in combination with the catalyst compositions comprising theshaped porous carbon product comprising carbon black have been found topermit oxidation at temperatures in excess of 140° C. (e.g., 140° toabout 150° C.).

Oxidation of glucose to glucaric acid can also be conducted in theabsence of nitrogen as an active reaction constituent. Some processesemploy nitrogen compounds such as nitric acid as an oxidant. The use ofnitrogen in a form in which it is an active reaction constituent, suchas nitrate or nitric acid, results in the need for NO_(x) abatementtechnology and acid regeneration technology, both of which addsignificant cost to the production of glucaric acid from these knownprocesses, as well as providing a corrosive environment which maydeleteriously affect the equipment used to carry out the process. Bycontrast, for example, in the event air or oxygen-enriched air is usedin the oxidation reaction of the present invention as the source ofoxygen, the nitrogen is essentially an inactive or inert constituent.Thus, an oxidation reaction employing air or oxygen-enriched air is areaction conducted essentially free of nitrogen in a form in which itwould be an active reaction constituent.

In accordance with various embodiments, glucose is oxidized to glucaricacid in the presence of a catalyst composition comprising the shapedporous carbon product as a catalyst support described herein and acatalytically active component at a surface of the support. In certainembodiments the catalytically active component comprises platinum. Insome embodiments, the catalytically active component comprises platinumand gold.

Applicants have discovered that oxidation catalyst compositionscomprising the shaped porous carbon product of the present inventionprovide unexpectedly greater selectivity and yield for producingglucaric acid from glucose when compared to similar catalysts comprisingsimilar support materials such as activated carbon. In particular,applicants have unexpectedly found that enhanced selectivity and yieldfor glucaric acid can be achieved by use of an oxidation catalystcomposition comprising the shaped porous carbon product as a catalystsupport and a catalytically active component comprising platinum andgold at a surface of the shaped porous carbon product (i.e., at asurface of the catalyst support). The enhanced glucaric acid yield istypically at least about 30%, at least about 35%, at least about 40%, atleast about, 45%, or at least about 50% (e.g., from about 35% to about65%, from about 40% to about 65%, or from about 45% to about 65%).Further, the enhanced glucaric acid selectivity is typically at leastabout 70%, at least about 75%, or at least about 80%.

The oxidation catalyst can include any of the shaped porous carbonproducts as described herein. For example, in various embodiments, theshaped porous carbon product comprises (a) carbon black and (b) acarbonized binder comprising a carbonization product of a water solubleorganic binder, wherein the shaped porous carbon product has a BETspecific surface area from about 20 m²/g to about 500 m²/g or from about25 m²/g to about 250 m²/g, a mean pore diameter greater than about 10nm, a specific pore volume greater than about 0.1 cm³/g, a radial piececrush strength greater than about 4.4 N/mm (1 lb/mm), and a carbon blackcontent of at least about 35 wt. %. In other embodiments, the shapedporous carbon product comprises a carbon agglomerate, wherein the shapedporous carbon product has a diameter of at least about 50 μm, a BETspecific surface area from about 20 m²/g to about 500 m²/g or from about25 m²/g to about 250 m²/g, a mean pore diameter greater than about 10nm, a specific pore volume greater than about 0.1 cm³/g, and a radialpiece crush strength greater than about 4.4 N/mm (1 lb/mm). Anothershaped porous carbon product in accordance with the present inventionalso has a pore volume measured on the basis of pores having a diameterfrom 1.7 nm to 100 nm and at least about 35% of the pore volume isattributable to pores having a pore diameter in the range of from about10 nm to about 50 nm.

Shaped porous carbon products suitable for use as catalyst supports inthe catalytic oxidation of glucaric acid include those which comprise(a) carbon black and (b) a carbonized binder comprising a carbonizationproduct of a water soluble organic binder, wherein the shaped porouscarbon product has a BET specific surface area from about 25 m²/g toabout 100 m²/g or from about 30 m²/g to about 75 m²/g, a mean porediameter greater than about 30 nm (e.g., from about 30 nm to about 75nm), and a radial piece crush strength greater than about 8.8 N/mm (2lb/mm). In some embodiments, shaped porous carbon products used ascatalyst supports in the catalytic oxidation of glucaric acid comprise acarbon agglomerate, wherein the shaped porous carbon product has adiameter of at least about 50 μm, BET specific surface area from about25 m²/g to about 100 m²/g or from about 30 m²/g to about 75 m²/g, a meanpore diameter greater than about 30 nm (e.g., from about 30 nm to about75 nm), and a radial piece crush strength greater than about 8.8 N/mm (2lb/mm). The carbon black content of these shaped porous carbon productsis typically at least about 50 wt. %, at least about 60 wt. %, at leastabout 70 wt. %, or at least about 80 wt. %.

In various embodiments, the catalytically active components orprecursors thereof comprising platinum and gold are in the formdescribed in U.S. Patent Application Publication 2011/0306790, theentire contents of which are incorporated herein by reference. Thispublication describes various oxidation catalysts comprising acatalytically active component comprising platinum and gold, which areuseful for the selective oxidation of compositions comprised of aprimary alcohol group and at least one secondary alcohol group (e.g.,glucose).

In various embodiments, an oxidation catalyst composition according thepresent invention comprises the shaped porous carbon product asdescribed herein as a catalyst support comprising particles of gold inthe form of a gold-containing alloy and particles consisting essentiallyof platinum (0) as the catalytically active components on a surface ofthe catalyst support. Typically, the total metal loading of the catalystcomposition is about 10 wt. % or less, from about 1 wt. % to about 8 wt.%, from about 1 wt. % to about 5 wt. %, or from about 2 wt. % to about 4wt. %.

In order to oxidize glucose to glucaric acid, a sufficient amount of thecatalytically active component must be present relative to the amount ofreactant (i.e., glucose). Accordingly, in a process of the presentinvention for the oxidation of glucose to glucaric acid as describedherein where the catalytically active component comprises platinum,typically the mass ratio of glucose to platinum is from about 10:1 toabout 1000:1, from about 10:1 to about 500:1, from about 10:1 to about200:1, or from about 10:1 to about 100:1.

In various embodiments, the oxidation catalyst of the present inventionmay be prepared according to the following method. The gold component ofthe catalyst is typically added to the shaped porous carbon product as asolubilized constituent to enable the formation of a uniform suspension.A base is then added to the suspension in order to create an insolublegold complex which can be more uniformly deposited onto the support. Forexample, the solubilized gold constituent is provided to the slurry asgold salt, such as HAuCl4. Upon creation of a well dispersed,heterogeneous mixture, a base is added to the slurry to form aninsoluble gold complex which then deposits on the surface of the shapedporous carbon product. Although any base which can affect the formationof an insoluble gold complex is useable, bases such as KOH, NaOH aretypically employed. It may be desirable, though not required, to collectthe shaped porous carbon product on which has been deposited theinsoluble gold complex prior to adding the platinum-containingconstituent, which collection can readily be accomplished by any of avariety of means known in the art such as, for example, centrifugation.The collected solids may optionally be washed and then may be heated todry. Heating may also be employed so as to reduce the gold complex onthe support to gold (0). Heating may be conducted at temperaturesranging from about 60° C. (to dry) up to about 500° C. (at whichtemperature the gold can be effectively reduced). In variousembodiments, the heating step may be conducted in the presence of areducing or oxidizing atmosphere in order to promote the reduction ofthe complex to deposit the gold onto the support as gold (0). Heatingtimes vary depending upon, for example, the objective of the heatingstep and the decomposition rate of the base added to form the insolublecomplex, and the heating times can range from a few minutes to a fewdays. More typically, the heating time for the purpose of drying rangesfrom about 2 to about 24 hours and for reducing the gold complex is onthe order of about 1 to about 4 hours.

In various embodiments, the concentration of the shaped porous carbonproduct in the slurry can be in the range of about 1 to about 100 g ofsolid/liter of slurry, and in other embodiments the concentration can bein the range of about 5 to about 25 g of solid/liter of slurry.

Mixing of the slurry containing the soluble gold-containing compound iscontinued for a time sufficient to form at least a reasonably uniformsuspension. Appropriate times can range from minutes to a few hours.After addition of the base to convert the gold-containing compound to aninsoluble gold-containing complex, the uniformity of the slurry shouldbe maintained for a time sufficient to enable the insoluble complex tobe formed and deposit on the shaped porous carbon product. In variousembodiments, the time can range from a few minutes to several hours.

Platinum can be added to the shaped porous carbon product or slurrythereof after deposition of gold onto the shaped porous carbon productor after heat treatment to reduce the gold complex on the support togold (0). Alternatively, the platinum may be added to the shaped porouscarbon product or slurry thereof prior to the addition of thesolubilized gold compound provided the platinum present on the supportis in a form that will not be re-dissolved upon the addition of baseused to promote the deposition of gold onto the support. The platinum istypically added as a solution of a soluble precursor or as a colloid.Platinum may be added as a compound selected form the group of platinum(II) nitrate, platinum(IV) nitrate, platinum oxynitrate, platinum (II)acetylacetonate (acac), tetraamineplatinum (II) nitrate,tetraamineplatinum (II) hydrogenphosphate, tetraamineplatinum (II)hydrogencarbonate, tetraamineplatinum (II) hydroxide, H2PtCl6, PtCl4,Na2PtCl4, K2PtCl4, (NH4)2PtCl4, Pt(NH3)4Cl2, mixed Pt(NH3)xCly,K2Pt(OH)6, Na2Pt(OH)6, (NMe4)2Pt(OH)6, and (EA)2Pt(OH)6 whereEA=ethanolamine. More preferred compounds include platinum(II) nitrate,platinum(IV) nitrate, platinum(II) acetylacetonate (acac), tetraamineplatinum(II) hydroxide, K2PtCl4, and K2Pt(OH)6.

Subsequent to the addition of the platinum compound, the support slurryand platinum-containing compound is dried. Drying may be conducted atroom temperature or at a temperature up to about 120° C. Morepreferably, drying is conducted at a temperature in the range of about40° C. to about 80° C. and more preferably still at about 60° C. Thedrying step may be conducted for a period of time ranging from about afew minutes to a few hours. Typically, the drying time is in the rangeof about 6 hours to about 24 hours. The drying can also be done withcontinuous or staged temperature increase from about 60° C. to 120° C.on a band calciner or belt dryer (which is preferred for commercialapplications).

After drying the support having the platinum compound deposited thereon,it is subjected to at least one thermal treatment in order to reduceplatinum deposited as platinum (II) or platinum (IV) to platinum (0).The thermal treatment(s) can be conducted in air or in any reducing oroxidizing atmosphere. In various embodiments the thermal treatment(s) is(are) conducted under a forming gas atmosphere. Alternatively, a liquidreducing agent may be employed to reduce the platinum; for example,hydrazine or formaldehyde or formic acid or salts thereof (e.g., sodiumformate) or NaH2PO2 may be employed to effect the requisite reduction ofthe platinum. The atmosphere under which the thermal treatment isconducted is dependent upon the platinum compound employed, with theobjective being substantially converting the platinum on the support toplatinum (0).

The temperatures at which the thermal treatment(s) is (are) conductedgenerally range from about 150° C. to about 600° C. More typically, thetemperatures of the thermal treatment(s) range from about 200° C. toabout 500° C. and, preferably, the range is from about 200° C. to about400° C. The thermal treatment is typically conducted for a period oftime ranging from about 1 hour to about 8 hours or from about 1 hour toabout 3 hours.

In various embodiments, the metal(s) deposited on the shaped porouscarbon product for the oxidation catalyst form a shell at leastpartially covering the surface of the carbon product. In other words,metal deposited on the shaped porous carbon product coats externalsurfaces of the carbon product. In various embodiments, the metalpenetrates surficial pores of the shaped porous carbon product to form ashell layer (“egg shell”) with a thickness of from about 10 μm to about400 μm, or from about 50 μm to about 150 μm (e.g., about 100 μm). Incertain embodiments the shell may be produced sub-surface to produce a10 μm to about 400 μm sub-surface band containing the catalyticallyactive metals (“egg yolk”).

Catalytic Hydrodeoxygenation

One series of chemical transformations that the catalyst compositions ofthe present invention are suited for is the hydrodeoxygenation ofcarbon-hydroxyl groups to carbon-hydrogen groups in a liquid or gaseousreaction medium. For example, one series of chemical transformation thatthe catalyst compositions of the present invention are especially suitedfor is the selective halide-promoted hydrodeoxygenation of an aldaricacid or salt, ester, or lactone thereof to a dicarboxylic acid.Accordingly, catalyst compositions of the present invention as describedherein can be utilized as hydrodeoxygenation catalysts. As such, thepresent invention is also directed to a process for the selective halidepromoted hydrodeoxygenation of an aldaric acid comprising reacting thealdaric acid or salt, ester, or lactone thereof with hydrogen in thepresence of a halogen-containing compound and a catalyst composition asdescribed herein to form a dicarboxylic acid. Typically, the catalystcomposition comprises at least one noble metal as a catalytically activecomponent.

The catalyst compositions of the present invention have been found to beespecially selective for halide-promoted hydrodeoxygenation of glucaricacid or salt, ester, or lactone thereof to adipic acid. U.S. Pat. No.8,669,397, referenced above and incorporated herein by reference,describes the chemocatalytic processes for the hydrodeoxygenation ofglucaric acid to adipic acid.

Adipic acid or salts and esters thereof may be prepared by reacting, inthe presence of a hydrodeoxygenation catalyst and a halogen source,glucaric acid or salt, ester, or lactone thereof, and hydrogen,according to the following reaction:

In the above reaction, glucaric acid or salt, ester, or lactone thereofis converted to an adipic acid product by catalytic hydrodeoxygenationin which carbon-hydroxyl groups are converted to carbon-hydrogen groups.In various embodiments, the catalytic hydrodeoxygenation ishydroxyl-selective wherein the reaction is completed without substantialconversion of the one or more other non-hydroxyl functional group of thesubstrate.

The halogen source may be in a form selected from the group consistingof ionic, molecular, and mixtures thereof. Halogen sources includehydrohalic acids (e.g., HCl, HBr, HI and mixtures thereof; preferablyHBr and/or HI), halide salts, (substituted or unsubstituted) alkylhalides, or molecular (diatomic) halogens (e.g., chlorine, bromine,iodine or mixtures thereof preferably bromine and/or iodine). In variousembodiments the halogen source is in diatomic form, hydrohalic acid, orhalide salt and, more preferably, diatomic form or hydrohalic acid. Incertain embodiments, the halogen source is a hydrohalic acid, inparticular hydrogen bromide.

Generally, the molar ratio of halogen to the glucaric acid or salt,ester, or lactone thereof is about equal to or less than about 1. Invarious embodiments, the mole ratio of halogen to the glucaric acid orsalt, ester, or lactone thereof is typically from about 1:1 to about0.1:1, more typically from about 0.7:1 to about 0.3:1, and still moretypically about 0.5:1.

Often, the reaction allows for recovery of the halogen source andcatalytic quantities (where molar ratio of halogen to the glucaric acidor salt, ester, or lactone thereof is less than about 1) of halogen canbe used, recovered and recycled for continued use as a halogen source.

Generally, the temperature of the hydrodeoxygenation reaction mixture isat least about 20° C., typically at least about 80° C., and moretypically at least about 100° C. In various embodiments, the temperatureof the hydrodeoxygenation reaction is maintained in the range of fromabout 20° C. to about 250° C., from about 80° C. to about 200° C., fromabout 120° C. to about 180° C., or from about 140° C. to 180° C.Typically, the partial pressure of hydrogen is at least about 25 psia(172 kPa), more typically at least about 200 psia (1379 kPa) or at leastabout 400 psia (2758 kPa). In various embodiments, the partial pressureof hydrogen is from about 25 psia (172 kPa) to about 2500 psia (17237kPa), from about 200 psia (1379 kPa) to about 2000 psia (13790 kPa), orfrom about 400 psia (2758 kPa) to about 1500 psia (10343 kPa).

The hydrodeoxygenation reaction may be conducted in the presence of asolvent. Solvents suitable for the selective hydrodeoxygenation reactioninclude water, carboxylic acids, amides, esters, lactones, sulfoxides,sulfones and mixtures thereof. Preferred solvents include water,mixtures of water and weak carboxylic acid, and weak carboxylic acid. Apreferred weak carboxylic acid is acetic acid.

Applicants have discovered that hydrodeoxygenation catalyst compositionscomprising the shaped porous carbon product of the present inventionprovide enhanced selectivity and yield for producing adipic acid. Inparticular, applicants have unexpectedly found that enhanced selectivityand yield for adipic acid can be achieved by use of a catalystcomposition comprising the shaped porous carbon product of the presentinvention as a catalyst support and a catalytically active component ata surface of the shaped porous carbon product (i.e., at a surface of thecatalyst support).

The catalyst can include any of the shaped porous carbon products asdescribed herein. For example, in various embodiments, the shaped porouscarbon product comprises (a) carbon black and (b) a carbonized bindercomprising a carbonization product of a water soluble organic binder,wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g or from about 25 m²/g to about 250m²/g, a mean pore diameter greater than about 5 nm, a specific porevolume greater than about 0.1 cm³/g, a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), and a carbon black content of atleast about 35 wt. %. In other embodiments, the shaped porous carbonproduct comprises a carbon agglomerate, wherein the shaped porous carbonproduct has a diameter of at least about 50 μm, a BET specific surfacearea from about 20 m²/g to about 500 m²/g or from about 25 m²/g to about250 m²/g, a mean pore diameter greater than about 5 nm, a specific porevolume greater than about 0.1 cm³/g, and a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm). Another shaped porous carbonproduct in accordance with the present invention also has a pore volumemeasured on the basis of pores having a diameter from 1.7 nm to 100 nmand at least about 35% of the pore volume is attributable to poreshaving a pore diameter in the range of from about 10 nm to about 50 nm.

The catalytically active component or precursor thereof may includenoble metals selected from the group consisting of ruthenium, rhodium,palladium, platinum, and combinations thereof. In various embodiments,the hydrodeoxygenation catalyst comprises two or more metals. Forexample, in some embodiments, the first metal is selected from the groupconsisting of cobalt, nickel, ruthenium, rhodium, palladium, osmium,iridium, and platinum (more particularly, ruthenium, rhodium, palladium,and platinum) and the second metal is selected from the group consistingof titanium, vanadium, chromium, manganese, iron, cobalt, nickel,copper, molybdenum, ruthenium, rhodium, palladium, silver, tungsten,iridium, platinum, and gold (more particularly, molybdenum, ruthenium,rhodium, palladium, iridium, platinum, and gold). In select embodiments,the first metal is selected from the group of platinum, rhodium andpalladium, and the second metal is selected from the group consisting ofruthenium, rhodium, palladium, platinum, and gold. In certainembodiments, the first metal is platinum and the second metal isrhodium. In these and other embodiments, the platinum to rhodium molarratio of the catalyst composition of the present invention is in therange of from about 3:1 to about 1:2 or from about 3:1 to about 1:1.

In various embodiments, the metal(s) deposited on the shaped porouscarbon product for the hydrodeoxygenation catalyst form a shell at leastpartially covering the surface of the carbon product. In other words,metal deposited on the shaped porous carbon product coats externalsurfaces of the carbon product. In various embodiments, the metalpenetrates surficial pores of the shaped porous carbon product to form ashell layer (“egg shell”) with a thickness of from about 10 μm to about400 μm, or from about 50 μm to about 150 μm (e.g., about 100 μm). Incertain embodiments the shell may be produced sub-surface to produce a10 μm to about 400 μm sub-surface band containing the catalyticallyactive metals (“egg yolk”).

Hydrodeoxygenation of 1,2,6-Hexanetriol

Another chemical transformation that the catalyst compositions of thepresent invention are advantageously used for is the selectivehydrodeoxygenation of 1,2,6-hexanetriol to 1,6-hexanediol (HDO) and1,2,5,6-hexanetetraol to 1,6-HDO). Accordingly, one process of thepresent invention is directed to the selective hydrodeoxygenation of1,2,6-hexanetriol comprising reacting 1,2,6-hexanetriol with hydrogenthe presence of a catalyst composition as disclosed herein to form HDO.In embodiments of this process, the catalytically active component ofthe catalyst composition comprises platinum. In some embodiments, thecatalytically active component of the catalyst composition comprisesplatinum and at least one metal (M2) selected from the group ofmolybdenum, lanthanum, samarium, yttrium, tungsten, and rhenium. Incertain embodiments, the catalytically active component of the catalystcomposition comprises platinum and tungsten.

Typically, the total weight of metal(s) is from about 0.1% to about 10%,or from 0.2% to 10%, or from about 0.2% to about 8%, or from about 0.2%to about 5%, of the total weight of the catalyst. In more preferredembodiments the total weight of metal of the catalyst is less than about4%. The molar ratio of platinum to (M2) may vary, for example, fromabout 20:1 to about 1:10. In various embodiments, the M1:M2 molar ratiois in the range of from about 10:1 to about 1:5. In still more preferredembodiments, the ratio of M1:M2 is in the range of about 8:1 to about1:2.

Typically, the conversion of 1,2,6-hexanetriol to HDO is conducted at atemperature in the range of from about 60° C. to about 200° C. or about120° C. to about 180° C. and a partial pressure of hydrogen in the rangeof from about 1480 kPa (200 psig) to about 13890 kPa (2000 psig) or fromabout 3550 kPa (500 psig) to about 13890 kPa (2000 psig).

Catalytic Amination of 1,6-Hexanediol

Furthermore, the catalyst compositions of the present invention are alsouseful for the selective amination of 1,6-hexanediol (HDO) to1,6-hexamethylenediamine (HMDA). Accordingly, another process of thepresent invention is directed to the selective amination of1,6-hexanediol to 1,6-hexamethylenediamine comprising reacting the HDOwith an amine in the presence of a catalyst composition as disclosedherein. In various embodiments of this process, the catalytically activecomponent of the catalyst composition comprises ruthenium.

In some embodiments of this process, the catalytically active componentof the catalyst composition comprises ruthenium and optionally a secondmetal such as rhenium or nickel. One or more other d-block metals, oneor more rare earth metals (e.g., lanthanides), and/or one or more maingroup metals (e.g., Al) may also be present in combination withruthenium and with ruthenium and rhenium combinations. In selectembodiments, the catalytically active phase consists essentially ofruthenium and rhenium. Typically, the total weight of metal(s) is in therange of from about 0.1% to about 10%, from about 1% to about 6%, orfrom about 1% to about 5% of the total weight of the catalystcomposition.

When the catalysts of the present invention comprise ruthenium andrhenium in combination, the molar ratio of ruthenium to rhenium isimportant. A by-product of processes for converting HDO to HMDA ispentylamine. Pentylamine is an off path by-product of the conversion ofHDO to HMDA that cannot be converted to HMDA or to an intermediate whichcan, on further reaction in the presence of the catalysts of the presentinvention, be converted to HMDA. However, the presence of too muchrhenium can have an adverse effect on the yield of HMDA per unit areatime (commonly known as space time yield, or STY). Therefore, the molarratio of ruthenium:rhenium should be maintained in the range of fromabout 20:1 to about 4:1. In various embodiments, the ruthenium:rheniummolar ratio is in the range of from about 10:1 to about 4:1 or fromabout 8:1 to about 4:1. In some embodiments, the ruthenium:rhenium molarratio of from about 8:1 to about 4:1 produces HMDA in at least 25% yieldwith an HMDA/pentylamine ratio of at least 20:1, at least 25:1, or atleast 30:1.

In accordance with the present invention, HDO is converted to HMDA byreacting HDO with an amine, e.g., ammonia, in the presence of thecatalysts of the present invention. Generally, in some embodiments, theamine may be added to the reaction in the form of a gas or liquid.Typically, the molar ratio of ammonia to HDO is at least about 40:1, atleast about 30:1, or at least about 20:1. In various embodiments, it isin the range of from about 40:1 to about 5:1, from about 30:1 to about10:1. The reaction of HDO with amine in the presence of the catalystcomposition of the present invention is carried out at a temperatureless than or equal to about 200° C. In various embodiments, the catalystcomposition is contacted with HDO and amine at a temperature less thanor equal to about 100° C. In some embodiments, the catalyst is contactedwith HDO and amine at a temperature in the range of from about 100° C.to about 180° C. or from about 140° C. to about 180° C.

Generally, in accordance with the present invention, the reaction isconducted at a pressure not exceeding about 10440 kPa (1500 psig). Invarious embodiments, the reaction pressure is in the range of from about1480 kPa (200 psig) to about 10440 kPa (1500 psig). In otherembodiments, and a pressure in the range of from about 2860 kPa (400psig) to about 8380 kPa (1200 psig). In certain preferred embodiments,the pressure in the range of about 2860 kPa (400 psig) to about 7000 kPa(1000 psig). In some embodiments, the disclosed pressure ranges includesthe pressure of NH₃ gas and an inert gas, such as N₂. In someembodiments, the pressure of NH₃ gas is in the range of from about450-1140 kPa (50-150 psig) and an inert gas, such as N₂ is in the rangeof from about 4930 kPa (700 psig) to about 10100 kPa (1450 psig).

In some embodiments, the catalyst is contacted with HDO and ammonia at atemperature in the range of from about 100° C. to about 180° C. and apressure in the range of from about 1480 kPa (200 psig) to about 10440kPa (1500 psig). In other embodiments, the catalyst is contacted withHDO and ammonia at a temperature in the range of about 140° C. to about180° C. and a pressure in the range of about 2860 kPa (400 psig) toabout 8380 kPa (1200 psig). In some embodiments, the disclosed pressureranges includes the pressure of NH₃ gas and an inert gas, such as N₂. Insome embodiments, the pressure of NH₃ gas is in the range of about450-1140 kPa 50-150 psig and an inert gas, such as N₂ is in the range ofabout 3550 kPa (500 psig) to about 10100 kPa (1450 psig).

The process of the present invention may be carried out in the presenceof hydrogen. Typically, in those embodiments in which the HDO and amineare reacted in the presence of hydrogen and the catalyst of the presentinvention, the hydrogen partial pressure is equal to or less than about790 kPa (100 psig).

The conversion of HDO to HMDA can also be conducted in the presence of asolvent. Solvents suitable for use in conjunction with the conversion ofHDO to HMDA in the presence of the catalysts of the present inventionmay include, for example, water, alcohols, esters, ethers, ketones, ormixtures thereof. In various embodiments, the preferred solvent iswater.

The chemocatalytic conversion of HDO to HMDA is likely to produce one ormore by-products such as, for example, pentylamine and hexylamine.By-products which are subsequently convertible to HMDA by furtherreaction in the presence of catalysts of the present invention areconsidered on-path by-products. Other by-products such as, for example,pentylamine and hexylamine are considered off path by-products for thereasons above discussed. In accordance with the present invention, atleast 20%, at least 30%, at least 40%, at least 50%, at least 60%, or atleast 70% of the product mixture resulting from a single pass reactionof HDO with amine (e.g., ammonia) in the presence of the catalysts ofthe present invention is HMDA.

The product mixture may be separated into one or more products by anysuitable methods known in the art. In some embodiments, the productmixture can be separated by fractional distillation under subatmosphericpressures. For example, in some embodiments, HMDA can be separated fromthe product mixture at a temperature between about 180° C. and about220° C. The HDO may be recovered from any remaining other products ofthe reaction mixture by one or more conventional methods known in theart including, for example, solvent extraction, crystallization orevaporative processes. The on-path by-products can be recycled to thereactor employed to produce the product mixture or, for example,supplied to a second reactor in which the on path by-products arefurther reacted with ammonia in the presence of the catalysts of thepresent invention to produce additional HMDA.

Embodiments

For further illustration, additional non-limiting embodiments of thepresent disclosure are set forth below.

Embodiment A1 is a process for preparing a shaped porous carbon product,the process comprising mixing water, a carbonaceous material, and anorganic binder to form a carbon-binder mixture, wherein the bindercomprises: (i) a saccharide selected from the group consisting of amonosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and/or (ii) a water solublepolymer; forming the carbon-binder mixture to produce a shaped carboncomposite; and heating the shaped carbon composite in a heating zone tocarbonize the binder thereby producing the shaped porous carbon product,wherein the heating zone comprises at least two heating stages that areeach maintained at an approximately constant temperature and thetemperature of each stage differs by at least about 50° C., at leastabout 100° C., at least about 150° C., at least about 200° C., at leastabout 250° C., at least about 300° C., at least about 350° C., or atleast about 400° C. with the temperature increasing from one stage tothe next.

Embodiment A2 is the process of embodiment Al wherein the temperature ofeach stage differs by from about 50° C. to about 500° C., from about100° C. to about 500° C., from about 200° C. to about 500° C., fromabout 300° C. to about 500° C., from about 50° C. to about 400° C., fromabout 100° C. to about 400° C., from about 150° C. to about 400° C.,from about 200° C. to about 400° C., from about 300° C. to about 400°C., from about 50° C. to about 300° C., from about 100° C. to about 300°C., from about 150° C. to about 300° C., or from about 200° C. to about300° C.

Embodiment A3 is the process of embodiment A1 or A2 wherein the heatingzone comprises at least three, at least four, at least five, or at leastsix heating stages that are each maintained at an approximately constanttemperature and the temperature of each stage independently differs byat least about 50° C., at least about 100° C., at least about 150° C.,at least about 200° C., at least about 250° C., at least about 300° C.,at least about 350° C., or at least about 400° C. from the precedingstage.

Embodiment A4 is a process for preparing a shaped porous carbon product,the process comprising mixing water, a carbonaceous material, and anorganic binder to form a carbon-binder mixture, wherein the bindercomprises: (i) a saccharide selected from the group consisting of amonosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and/or (ii) a water solublepolymer; forming the carbon-binder mixture to produce a shaped carboncomposite; and heating the shaped carbon composite in a heating zone tocarbonize the binder thereby producing the shaped porous carbon product,wherein the heating zone comprises: (1) a first heating stage where theshaped carbon composite is heated at a first temperature; and (2) asecond heating stage where the shaped carbon composite is heated at asecond temperature and wherein the first and second temperature are eachapproximately constant and the second temperature is greater than thefirst temperature by at least about 50° C., at least about 100° C., atleast about 150° C., at least about 200° C., at least about 250° C., atleast about 300° C., at least about 350° C., or at least about 400° C.

Embodiment A5 is the process of embodiment A4 wherein the temperature ofthe first heating stage temperature and the second stage heating stagediffer by from about 50° C. to about 500° C., from about 100° C. toabout 500° C., from about 200° C. to about 500° C., from about 300° C.to about 500° C., from about 50° C. to about 400° C., from about 100° C.to about 400° C., from about 150° C. to about 400° C., from about 200°C. to about 400° C., from about 300° C. to about 400° C., from about 50°C. to about 300° C., from about 100° C. to about 300° C., from about150° C. to about 300° C., or from about 200° C. to about 300° C.

Embodiment A6 is the process of embodiment A4 or A5 wherein the heatingzone comprises a third heating stage where the shaped carbon compositeis heated at a third temperature that is approximately constant and isgreater than the second heating stage temperature by at least about 50°C., at least about 100° C., at least about 150° C., at least about 200°C., at least about 250° C., at least about 300° C., at least about 350°C., or at least about 400° C.

Embodiment A7 is the process of embodiment A6 wherein the temperature ofthe second heating stage temperature and the third stage heating stagetemperature differ by from about 50° C. to about 500° C., from about100° C. to about 500° C., from about 200° C. to about 500° C., fromabout 300° C. to about 500° C., from about 50° C. to about 400° C., fromabout 100° C. to about 400° C., from about 150° C. to about 400° C.,from about 200° C. to about 400° C., from about 300° C. to about 400°C., from about 50° C. to about 300° C., from about 100° C. to about 300°C., from about 150° C. to about 300° C., or from about 200° C. to about300° C.

Embodiment A8 is the process of any one of embodiments A1 to A7 whereinthe heating zone comprises a multi-stage continuous rotary kiln.

Embodiment A9 is a process for preparing a shaped porous carbon product,the process comprising mixing water, a carbonaceous material, and anorganic binder to form a carbonaceous material mixture, wherein thebinder comprises: (i) a saccharide selected from the group consisting ofa monosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and/or (ii) a water solublepolymer; forming the carbonaceous material mixture to produce a shapedcarbon composite; and heating the shaped carbon composite in a heatingzone to carbonize the binder thereby producing the shaped porous carbonproduct, wherein the heating zone comprises a continuous rotary kiln.

Embodiment A10 is the process of any one of embodiments A1 to A9 whereinthe process further comprises drying the shaped carbon composite at atemperature from about 90° C. to about 150° C., from about 100° C. toabout 150° C., or from about 100° C. to about 140° C., wherein the watercontent of the shaped carbon composite after drying is no greater thanabout 15 wt. %, no greater than about 12 wt. %, or no greater than about10 wt. %.

Embodiment A11 is a process for preparing a shaped porous carbonproduct, the process comprising mixing water, a carbonaceous material,and an organic binder to form a carbon-binder mixture, wherein thebinder comprises: (i) a saccharide selected from the group consisting ofa monosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and/or (ii) a water solublepolymer; forming the carbon-binder mixture to produce a shaped carboncomposite; drying the shaped carbon composite at a temperature fromabout 90° C. to about 150° C., from about 100° C. to about 150° C., orfrom about 100° C. to about 140° C., wherein the water content of theshaped carbon composite after drying is no greater than about 15 wt. %,no greater than about 12 wt. %, or no greater than about 10 wt. %; andheating the shaped carbon composite in a heating zone to carbonize thebinder thereby producing the shaped porous carbon product.

Embodiment A12 is the process of embodiment A10 or A11 wherein the watercontent of the shaped carbon composite after drying is from about 2 wt.% to about 15 wt. %, from about 2 wt. % to about 12 wt. %, from about 2wt. % to about 10 wt. %, from about 4 wt. % to about 15 wt. %, fromabout 4 wt. % to about 12 wt. %, from about 4 wt. % to about 10 wt. %,from about 5 wt. % to about 15 wt. %, from about 5 wt. % to about 12 wt.%, or from about 5 wt. % to about 10 wt. %.

Embodiment A13 is the process of any one of embodiments A10 to A12wherein drying is conducted over a period of time that is no more thanabout 120 minutes, no more than about 90 minutes, or no more than about75 minutes, or from about 30 minutes to about 120 minutes, from about 30minutes to about 90 minutes, from about 30 minutes to about 75 minutes,from about 60 minutes to about 120 minutes, or from about 60 minutes toabout 90 minutes.

Embodiment A14 is the process of any one of embodiments A10 to A13wherein drying is performed using a continuous belt dryer.

Embodiment A15 is the process of any one of embodiments A1 to A14wherein the binder comprises a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof.

Embodiment A16 is the process of any one of embodiments A1 to A14wherein the binder comprises: (i) a saccharide selected from the groupconsisting of a monosaccharide, a disaccharide, an oligosaccharide, aderivative thereof, and any combination thereof and (ii) a water solublepolymer.

Embodiment A17 is a process for preparing a shaped porous carbonproduct, the process comprising mixing water, a carbonaceous material,and an organic binder to form a carbon-binder mixture, wherein thebinder comprises: (i) a saccharide selected from the group consisting ofa monosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and (ii) a water soluble polymer,wherein a 2 wt. % aqueous solution or a 5 wt. % aqueous solution of thewater soluble polymer has a viscosity of no greater than about 500mPa·s, no greater than about 400 mPa·s, no greater than about 300 mPa·s,no greater than about 200 mPa·s, no greater than about 100 mPa·s, nogreater than about 75 mPa·s, or no greater than about 50 mPa·s at 25° C.and/or the water soluble polymer has a number average molecular weight(M_(n)) that is no greater than about 50,000 g/mol, no greater thanabout 40,000 g/mol, no greater than about 30,000 g/mol, no greater thanabout 25,000 g/mol, or no greater than about 20,000 g/mol; forming thecarbon-binder mixture to produce a shaped carbon composite; and heatingthe shaped carbon composite in a heating zone to carbonize the binderthereby producing the shaped porous carbon product.

Embodiment A18 is the process of embodiment A17 wherein the processfurther comprises drying the shaped carbon composite at a temperaturefrom about 90° C. to about 150° C., wherein the water content of theshaped carbon composite after drying is no greater than about 15 wt. %,no greater than about 12 wt. %, or no greater than about 10 wt. %.

Embodiment A19 is the process of embodiment A17 or A18 wherein the watercontent of the shaped carbon composite after drying is from about 2 wt.% to about 15 wt. %, from about 2 wt. % to about 12 wt. %, from about 2wt. % to about 10 wt. %, from about 4 wt. % to about 15 wt. %, fromabout 4 wt. % to about 12 wt. %, from about 4 wt. % to about 10 wt. %,from about 5 wt. % to about 15 wt. %, from about 5 wt. % to about 12 wt.%, or from about 5 wt. % to about 10 wt. %.

Embodiment A20 is the process of any one of embodiments A17 to A19wherein drying is performed using a continuous belt dryer.

Embodiment A21 is the process of any one of embodiments A17 to A20wherein drying is conducted over a period of time that is no more thanabout 120 minutes, no more than about 90 minutes, or no more than about75 minutes, or from about 30 minutes to about 120 minutes, from about 30minutes to about 90 minutes, from about 30 minutes to about 75 minutes,from about 60 minutes to about 120 minutes, or from about 60 minutes toabout 90 minutes.

Embodiment A22 is the process of any one of embodiments A1 to A21wherein a 2 wt. % aqueous solution or a 5 wt. % aqueous solution of thewater soluble polymer has a viscosity of no greater than about 500mPa·s, no greater than about 400 mPa·s, no greater than about 300 mPa·s,no greater than about 200 mPa·s, no greater than about 100 mPa·s, nogreater than about 75 mPa·s, or no greater than about 50 mPa·s at 25° C.

Embodiment A23 is the process of any one of embodiments A1 to A21wherein a 2 wt. % aqueous solution or a 5 wt. % aqueous solution of thewater soluble polymer has a viscosity that is from about 2 to about 500mPa·s, from about 2 to about 400 mPa·s, from about 2 to about 300 mPa·s,from about 2 to about 200 mPa·s, from about 2 to about 150 mPa·s, fromabout 2 to about 100 mPa·s, from about 2 to about 75 mPa·s, or fromabout 2 to about 50 mPa·s at 25° C.

Embodiment A24 is the process of any one of embodiments A1 to A23wherein the water soluble polymer has a number average molecular weight(M_(n)) that is no greater than about 50,000 g/mol, no greater thanabout 40,000 g/mol, no greater than about 30,000 g/mol, no greater thanabout 25,000 g/mol, or no greater than about 20,000 g/mol.

Embodiment A25 is the process of any one of embodiments A1 to A23wherein the water soluble polymer has a number average molecular weight(M_(n)) that is from about 2,000 to about 50,000 g/mol, from about 5,000to about 40,000 g/mol, from about 5,000 to about 30,000 g/mol, fromabout 5,000 to about 25,000 g/mol, from about 5,000 to about 20,000g/mol, from about 10,000 to about 50,000 g/mol, from about 10,000 toabout 40,000 g/mol, from about 10,000 to about 30,000 g/mol, from about10,000 to about 25,000 g/mol, or from about 10,000 to about 20,000g/mol.

Embodiment A26 is the process of embodiment A1 to A25 wherein the weightratio of (i) the saccharide to (ii) the water soluble polymer is fromabout 5:1 to about 100:1, from about 5:1 to about 50:1, 10:1 to about40:1, from about 10:1 to about 30:1, from about 10:1 to about 25:1, fromabout 10:1 to about 20:1, from about 20:1 to about 30:1, or from about25:1 to about 30:1

Embodiment A27 is the process of any one of embodiments A1 to A26wherein the carbonaceous material is selected from the group consistingof activated carbon, carbon black, graphite, and combinations thereof.

Embodiment A28 is the process of any one of embodiments A1 to A26wherein the carbonaceous material comprises carbon black.

Embodiment A29 is the process of any one of embodiments A1 to A28wherein the shaped carbon composite is heated to a final temperature ofat least about 400° C., at least about 500° C., at least about 600° C.,at least about 700° C., or at least about 800° C. in the heating zone.

Embodiment A30 is the process of any one of embodiments A1 to A28wherein the shaped carbon composite is heated to a final temperature offrom about 400° C. to about 1,000° C., from about 400° C. to about 900°C., from about 400° C. to about 850° C., from about 400° C. to about800° C., from about 500° C. to about 850° C., from about 500° C. toabout 800° C., from about 500° C. to about 700° C., from about 600° C.to about 850° C. or from about 600° C. to about 800° C. in the heatingzone.

Embodiment A31 is the process of any one of embodiments A1 to A30wherein the heating zone comprises a multi-stage continuous rotary kiln.

Embodiment A32 is the process of any one of embodiments A1 to A31wherein the shaped carbon composite is heated in an inert or oxidativeatmosphere.

Embodiment A33 is the process of embodiment A32 wherein the atmosphereis an inert atmosphere.

Embodiment A34 is the process of any one of embodiments A1 to A33wherein the shaped carbon composite is formed by extruding thecarbon-binder mixture.

Embodiment A35 is the process of any one of embodiments A1 to A34wherein the weight ratio of the binder to carbonaceous material in thecarbon-binder mixture is at least about 1:4, at least about 1:3, atleast about 1:2, at least about 1:1, or at least 1.5:1.

Embodiment A36 is the process of any one of embodiments A1 to A34wherein the weight ratio of binder to carbonaceous material in thecarbon-binder mixture is from about 1:4 to about 3:1, from about 1:4 toabout 1:1, from about 1:3 to about 2:1, from about 1:3 to about 1:1, orabout 1:1.

Embodiment A37 is the process of any one of embodiments A1 to A36wherein the carbonaceous material content of the carbon-binder mixtureis at least about 35 wt. %, at least about 40 wt. %, at least about 45wt. %, at least about 50 wt. %, at least about 55 wt. %, at least about60 wt. %, at least about 65 wt. %, or at least about 70 wt. % on a dryweight basis.

Embodiment A38 is the process of any one of embodiments A1 to A36wherein the carbonaceous material content of the carbon-binder mixtureis from about 35 wt. % to about 80 wt. %, from about 35 wt. % to about75 wt. %, from about 40 wt. % to about 80 wt. %, or from about 40 wt. %to about 75 wt. % on a dry weight basis.

Embodiment A39 is the process of any one of embodiments A1 to A38wherein the concentration of the binder in the carbon-binder mixture isat least about 10 wt. %, at least about 20 wt. %, at least about 25 wt.%, at least about 30 wt. %, at least about 35 wt. %, at least about 40wt. %, or at least 45 wt. % binder on a dry weight basis.

Embodiment A40 is the process of any one of embodiments A1 to A38wherein the concentration of the binder in the carbon-binder mixture isfrom about 10 wt. % to about 50 wt. %, from about 10 wt. % to about 45wt. %, from about 15 wt. % to about 50 wt. %, from about 20 wt. % toabout 50 wt. %, or from about 20 wt. % to about 45 wt. % on a dry weightbasis.

Embodiment A41 is the process of any one of embodiments A1 to A40wherein the water content of the carbon-binder mixture is no more thanabout 80% by weight, no more than about 55% by weight, no more thanabout 40% by weight, or no more than about 25% by weight.

Embodiment A42 is the process of any one of embodiments A1 to A40wherein the water content of the carbon-binder mixture is from about 5wt. % to about 80 wt. % , from about 5 wt. % to about 55 wt. %, fromabout 5 wt. % to about 40 wt. % or from about 5 wt. % to about 25 wt. %.

Embodiment A43 is the process of any one of embodiments A1 to A42wherein the binder comprises a monosaccharide.

Embodiment A44 is the process of any one of embodiments A1 to A43wherein the monosaccharide is selected from the group consisting ofglucose, fructose, hydrate thereof, syrup thereof, and combinationsthereof.

Embodiment A45 is the process of any one of embodiments A1 to A44wherein the binder comprises a disaccharide.

Embodiment A46 is the process of any one of embodiments A1 to A45wherein the disaccharide is selected from the group consisting ofmaltose, sucrose, syrup thereof, and combinations thereof.

Embodiment A47 is the process of any one of embodiments A1 to A46wherein the water soluble polymer comprises a polymeric carbohydrate, aderivative of a polymeric carbohydrate, or a non-carbohydrate syntheticpolymer, or any combination thereof.

Embodiment A48 is the process of any one of embodiments A1 to A47wherein the binder comprises a polymeric carbohydrate, derivative of apolymeric carbohydrate, or any combination thereof.

Embodiment A49 is the process of embodiment A47 or A48 wherein thepolymeric carbohydrate or derivative of the polymeric carbohydratecomprises a cellulosic compound.

Embodiment A50 is the process of embodiment A49 wherein the cellulosiccompound is selected from the group consisting of methylcellulose,ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose,hydroxypropylcellulose, methylhydroxyethylcellulose,ethylhydroxyethylcellulose, hydroxypropylmethylcellulose,carboxymethylcellulose, and mixtures thereof.

Embodiment A51 is the process of embodiment A49 wherein the cellulosiccompound comprises hydroxyethylcellulose.

Embodiment A52 is the process of any one of embodiments A47 to A51wherein the polymeric carbohydrate or derivative of the polymericcarbohydrate derivative is selected from the group consisting of alginicacid, pectin, aldonic acids, aldaric acids, uronic acids, sugaralcohols, and salts, oligomers, and polymers thereof.

Embodiment A53 is the process of any one of embodiments A47 to A52wherein the polymeric carbohydrate or derivative of the polymericcarbohydrate comprises a starch.

Embodiment A54 is the process of any one of embodiments A47 A53 whereinthe polymeric carbohydrate or derivative of the polymeric carbohydratecomprises a soluble gum.

Embodiment A55 is the process of any one of embodiments A47 to A54,wherein the binder comprises a non-carbohydrate synthetic polymer.

Embodiment A56 is the process of any one of embodiments A47 to A55wherein the non-carbohydrate synthetic polymer is selected from thegroup consisting of polyacrylic acid, polyvinyl alcohols,polyvinylpyrrolidones, polyvinyl acetates, polyacrylates, polyethers,and copolymers derived therefrom.

Embodiment A57 is the process of any one of embodiments A1 to A56wherein the binder comprises a saccharide selected from the groupconsisting of glucose, fructose or hydrate thereof and a water solublepolymer selected from the group consisting of hydroxyethylcellulose,methylcellulose, and starch.

Embodiment A58 is the process of any one of embodiments A1 to A57wherein the shaped porous carbon product has a BET specific surface areafrom about 20 m²/g to about 500 m²/g, from about 20 m²/g to about 350m²/g, from about 20 m²/g to about 250 m²/g, from about 20 m²/g to about225 m²/g, from about 20 m²/g to about 200 m²/g, from about 20 m ²/g toabout 175 m²/g, from about 20 m²/g to about 150 m²/g, from about 20 m²/gto about 125 m²/g, or from about 20 m²/g to about 100 m²/g, from about25 m²/g to about 500 m²/g, from about 25 m²/g to about 350 m²/g, fromabout 25 m²/g to about 250 m²/g, from about 25 m ²/g to about 225 m²/g,from about 25 m²/g to about 200 m²/g, from about 25 m²/g to about 175m²/g, from about 25 m²/g to about 150 m²/g, from about 25 m²/g to about125 m²/g, from about 25 m²/g to about 100 m²/g, from about 30 m²/g toabout 500 m²/g, from about 30 m ²/g to about 350 m²/g, from about 30m²/g to about 250 m²/g, from about 30 m²/g to about 225 m²/g, from about30 m²/g to about 200 m²/g, from about 30 m²/g to about 175 m²/g, fromabout 30 m²/g to about 150 m²/g, from about 30 m²/g to about 125 m²/g,or from about 30 m²/g to about 100 m²/g.

Embodiment A59 is the process of any one of embodiments A1 to A58wherein the shaped porous carbon product has a mean pore diametergreater than about 5 nm, greater than about 10 nm, greater than about 12nm, or greater than about 14 nm.

Embodiment A60 is the process of any one of embodiments A1 to A58wherein the shaped porous carbon product has a mean pore diameter fromabout 5 nm to about 100 nm, from about 5 nm to about 70 nm, from 5 nm toabout 50 nm, from about 5 nm to about 25 nm, from about 10 nm to about100 nm, from about 10 nm to about 70 nm, from 10 nm to about 50 nm, orfrom about 10 nm to about 25 nm.

Embodiment A61 is the process of any one of embodiments A1 to A60wherein the shaped porous carbon product has a specific pore volume ofthe pores having a diameter of 1.7 nm to 100 nm as measured by the BJHprocess that is greater than about 0.1 cm³/g, greater than about 0.2cm³/g, or greater than about 0.3 cm³/g.

Embodiment A62 is the process of any one of embodiments A1 to A60wherein the shaped porous carbon product has a specific pore volume ofthe pores having a diameter of 1.7 nm to 100 nm as measured by the BJHprocess that is from about 0.1 cm³/g to about 1.5 cm³/g, from about 0.1cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g to about 0.8 cm³/g, fromabout 0.1 cm³/g to about 0.7 cm³/g, from about 0.1 cm³/g to about 0.6cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, from about 0.2 cm³/g toabout 1 cm³/g, from about 0.2 cm³/g to about 0.9 cm³/g, from about 0.2cm³/g to about 0.8 cm³/g, from about 0.2 cm3/g to about 0.7 cm³/g, fromabout 0.2 cm³/g to about 0.6 cm³/g, from about 0.2 cm³/g to about 0.5cm³/g, from about 0.3 cm³/g to about 1 cm³/g, from about 0.3 cm³/g toabout 0.9 cm³/g, from about 0.3 cm³/g to about 0.8 cm³/g, from about 0.3cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g to about 0.6 cm³/g, orfrom about 0.3 cm³/g to about 0.5 cm³/g.

Embodiment A63 is the process of any one of embodiments A1 to A62wherein at least about 35%, at least about 40%, at least about 45%, orat least about 50% of the pore volume of the shaped porous carbonproduct, as measured by the BJH process on the basis of pores having adiameter from 1.7 nm to 100 nm, is attributable to pores having a meanpore diameter of from about 10 nm to about 50 nm.

Embodiment A64 is the process of any one of embodiments A1 to A62wherein from about 35% to about 80%, from about 35% to about 75%, fromabout 35% to about 65%, from about 40% to about 80%, from about 40% toabout 75%, or from about 40% to about 70% of the pore volume of theshaped porous carbon product, as measured by the BJH process on thebasis of pores having a diameter from 1.7 nm to 100 nm, is attributableto pores having a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment A65 is the process of any one of embodiments A1 to A64wherein at least about 50%, at least about 60%, at least about 70%, atleast about 80%, or at least about 90% of the pore volume of the shapedporous carbon product, as measured by the BJH process on the basis ofpores having a diameter from 1.7 nm to 100 nm, is attributable to poreshaving a mean pore diameter of from about 10 nm to about 100 nm.

Embodiment A66 is the process of any one of embodiments A1 to A64wherein from about 50% to about 95%, from about 50% to about 90%, fromabout 50% to about 80%, from about 60% to about 95%, from about 60% toabout 90%, from about 60% to about 80%, from about 70% to about 95%,from about 70% to about 90%, from about 70% to about 80%, from about 80%to about 95%, or from about 80% to about 90% of the pore volume of theshaped porous carbon product, as measured by the BJH process on thebasis of pores having a diameter from 1.7 nm to 100 nm, is attributableto pores having a mean pore diameter of from about 10 nm to about 100nm.

Embodiment A67 is the process of any one of embodiments A1 to A66wherein no more than about 10%, no more than about 5%, or no more thanabout 1% of the pore volume of the shaped porous carbon product, asmeasured by the BJH process on the basis of pores having a diameter from1.7 nm to 100 nm, is attributable to pores having a mean pore diameterless than 3 nm.

Embodiment A68 is the process of any one of embodiments A1 to A66wherein from about 0.1% to about 10%, from about 0.1% to about 5%, fromabout 0.1% to about 1%, from about 1% to about 10%, or from about 1% toabout 5% of the pore volume of the shaped porous carbon product, asmeasured by the BJH process on the basis of pores having a diameter from1.7 nm to 100 nm, is attributable to pores having a mean pore diameterless than 3 nm.

Embodiment A69 is the process of any one of embodiments A1 to A68wherein the shaped porous carbon product has a pore size distributionsuch that the peak of the distribution is at a diameter greater thanabout 5 nm, greater than about 7.5 nm, greater than about 10 nm, greaterthan about 12.5 nm, greater than about 15 nm, or greater than about 20nm.

Embodiment A70 is the process of any one of embodiments A1 to A69wherein the shaped porous carbon product has a pore size distributionsuch that the peak of the distribution is at a diameter less than about100 nm, less than about 90 nm, less than about 80 nm, or less than about70 nm.

Embodiment A71 is the process of any one of embodiments A1 to A70wherein the shaped porous carbon product has a radial piece crushstrength greater than about 4.4 N/mm (1 lb/mm), greater than about 8.8N/mm (2 lbs/mm), greater than about 13.3 N/mm (3 lbs/mm), greater thanabout 15 N/mm (3.4 lbs/mm), greater than about 17 N/mm (3.8 lbs/mm), orgreater than about 20 N/mm (4.5 lbs/mm).

Embodiment A72 is the process of any one of embodiments A1 to A70wherein the shaped porous carbon product has a radial piece crushstrength from about 4.4 N/mm (1 lb/mm) to about 88 N/mm (20 lbs/mm),from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15 lbs/mm), from about8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm), from about 15 N/mm (3.4lbs/mm) to about 88 N/mm (20 lbs/mm), from about 15 N/mm (3.4 lbs/mm) toabout 44 N/mm (10 lbs/mm), from about 17 N/mm (3.8 lbs/mm) to about 88N/mm (20 lbs/mm), from about 17 N/mm (3.8 lbs/mm) to about 44 N/mm (10lbs/mm), from about 20 N/mm (4.5 lbs/mm) to about 88 N/mm (20 lbs/mm),or from about 20 N/mm (4.5 lbs/mm) to about 44 N/mm (10 lbs/mm).

Embodiment A73 is the process of any one of embodiments A1 to A72wherein the shaped porous carbon product has a mechanical piece crushstrength greater than about 22 N (5 lbs), greater than about 36 N (8lbs), or greater than about 44 N (10 lbs).

Embodiment A74 is the process of any one of embodiments A1 to A72wherein the shaped porous carbon product has a mechanical piece crushstrength from about 22 N (5 lbs) to about 88 N (20 lbs), from about 22 N(5 lbs) to about 66 N (15 lbs), or from about 33 N (7.5 lbs) to about 66N (15 lbs).

Embodiment A75 is the process of any one of embodiments A1 to A74wherein the shaped porous carbon product has a diameter of at leastabout 50 μm, at least about 500 μm, at least about 1,000 μm, or at leastabout 10,000 μm.

Embodiment A76 is the process of any one of embodiments A1 to A75wherein the shaped porous carbon product has a carbonaceous materialcontent of at least about 35 wt. %, at least about 40 wt. %, at leastabout 45 wt. %, at least about 50 wt. %, at least about 55 wt. %, atleast about 60 wt. %, at least about 65 wt. %, or at least about 70 wt.%.

Embodiment A77 is the process of any one of embodiments A1 to A75wherein the shaped porous carbon product has a carbonaceous materialcontent from about 35 wt. % to about 80 wt. %, from about 35 wt. % toabout 75 wt. %, from about 40 wt. % to about 80 wt. %, or from about 40wt. % to about 75 wt. %.

Embodiment A78 is the process of any one of embodiments A1 to A77wherein the shaped porous carbon product has a carbonized binder contentfrom about 10 wt. % to about 50 wt. %, from about 20 wt. % to about 50wt. %, from about 25 wt. % to about 40 wt. %, or from about 25 wt. % toabout 35 wt. %.

Embodiment A79 is the process of any one of embodiments A1 to A78wherein the water soluble polymer constitutes no more than about 5 wt.%, no more than about 4 wt. %, no more than about 3 wt. %, no more thanabout 2 wt. % based on the weight of the water, saccharide and watersoluble polymer mixed with the carbonaceous material.

Embodiment A80 is the process of any one of embodiments A1 to A79wherein the water soluble polymer constitutes no more than about 5 wt.%, no more than about 4 wt. %, no more than about 3 wt. %, or no morethan about 2 wt. % based on the weight of the water, saccharide andwater soluble polymer mixed with the carbonaceous material.

Embodiment A81 is the process of any one of embodiments A1 to A79wherein the water soluble polymer constitutes from about 0.5 wt. % toabout 5 wt. %, from about 0.5 wt. % to about 4 wt. %, from about 0.5 wt.% to about 3 wt. %, from about 0.5 wt. % to about 2 wt. %, from about 1wt. % to about 5 wt. %, from about 1 wt. % to about 4 wt. %, from about1 wt. % to about 3 wt. %, or from about 1 wt. % to about 2 wt. % basedon the weight of the water, saccharide and water soluble polymer mixedwith the carbonaceous material.

Embodiment B1 is a shaped porous carbon product comprising: carbon blackand a carbonized binder comprising a carbonization product of an organicbinder, wherein the shaped porous carbon product has a BET specificsurface area from about 25 m²/g to about 500 m²/g, a mean pore diametergreater than about 10 nm, a specific pore volume greater than about 0.1cm³/g, a radial piece crush strength greater than about 4.4 N/mm (1lb/mm), greater than about 8.8 N/mm (2 lbs/mm), greater than about 13.3N/mm (3 lbs/mm), greater than about 15 N/mm (3.4 lbs/mm), greater thanabout 17 N/mm (3.8 lbs/mm), or greater than about 20 N/mm (4.5 lbs/mm),and a carbon black content of at least about 35 wt. %, and wherein theshaped porous carbon product has improved wettability as compared toshaped porous carbon product control 1.

Embodiment B2 is a highly wettable shaped porous carbon productcomprising a carbon agglomerate comprising a carbonaceous materialwherein the shaped porous carbon product has a mean diameter of at leastabout 50 μm, a BET specific surface area from about 25 m²/g to about 500m²/g, a mean pore diameter greater than about 10 nm, a specific porevolume greater than about 0.1 cm³/g, and a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), greater than about 8.8 N/mm (2lbs/mm), greater than about 13.3 N/mm (3 lbs/mm), greater than about 15N/mm (3.4 lbs/mm), greater than about 17 N/mm (3.8 lbs/mm), or greaterthan about 20 N/mm (4.5 lbs/mm), and wherein the shaped porous carbonproduct has improved wettability as compared to shaped porous carbonproduct control 1.

Embodiment B3 is the shaped porous carbon product of embodiment B2wherein the carbonaceous material is selected from the group consistingof activated carbon, carbon black, graphite, and combinations thereof.

Embodiment B4 is the shaped porous carbon product of embodiment B2wherein the carbonaceous material comprises carbon black.

Embodiment B5 is the shaped porous carbon product of any one ofembodiments B1 to B4 wherein the shaped porous carbon product has a BETspecific surface area from about 20 m²/g to about 500 m²/g, from about20 m²/g to about 350 m²/g, from about 20 m²/g to about 250 m²/g, fromabout 20 m²/g to about 225 m²/g, from about 20 m²/g to about 200 m²/g,from about 20 m²/g to about 175 m²/g, from about 20 m²/g to about 150m²/g, from about 20 m²/g to about 125 m²/g, or from about 20 m²/g toabout 100 m²/g, from about 25 m²/g to about 500 m²/g, from about 25 m²/gto about 350 m²/g, from about 25 m²/g to about 250 m²/g, from about 25m²/g to about 225 m²/g, from about 25 m²/g to about 200 m²/g, from about25 m²/g to about 175 m²/g, from about 25 m²/g to about 150 m²/g, fromabout 25 m²/g to about 125 m²/g, from about 25 m²/g to about 100 m²/g,from about 30 m²/g to about 500 m²/g, from about 30 m²/g to about 350m²/g, from about 30 m²/g to about 250 m²/g, from about 30 m²/g to about225 m²/g, from about 30 m²/g to about 200 m²/g, from about 30 m²/g toabout 175 m²/g, from about 30 m²/g to about 150 m²/g, from about 30 m²/gto about 125 m²/g, or from about 30 m²/g to about 100 m²/g.

Embodiment B6 is the shaped porous carbon product of any one ofembodiments B1 to B5 wherein the shaped porous carbon product has a meanpore diameter greater than about 5 nm, greater than about 10 nm, greaterthan about 12 nm, or greater than about 14 nm.

Embodiment B7 is the shaped porous carbon product of any one ofembodiments B1 to B5 wherein the shaped porous carbon product has a meanpore diameter from about 5 nm to about 100 nm, from about 5 nm to about70 nm, from 5 nm to about 50 nm, from about 5 nm to about 25 nm, fromabout 10 nm to about 100 nm, from about 10 nm to about 70 nm, from 10 nmto about 50 nm, or from about 10 nm to about 25 nm.

Embodiment B8 is the shaped porous carbon product of any one ofembodiments B1 to B7 wherein the shaped porous carbon product has aspecific pore volume of the pores having a diameter of 1.7 nm to100 nmas measured by the BJH process that is greater than about 0.1 cm³/g,greater than about 0.2 cm³/g, or greater than about 0.3 cm³/g.

Embodiment B9 is the shaped porous carbon product of any one ofembodiments B1 to B7 wherein the shaped porous carbon product has aspecific pore volume of the pores having a diameter of 1.7 nm to 100 nmas measured by the BJH process that is from about 0.1 cm³/g to about 1.5cm³/g, from about 0.1 cm³/g to about 0.9 cm³/g, from about 0.1 cm³/g toabout 0.8 cm³/g, from about 0.1 cm³/g to about 0.7 cm³/g, from about 0.1cm³/g to about 0.6 cm³/g, from about 0.1 cm³/g to about 0.5 cm³/g, fromabout 0.2 cm³/g to about 1 cm³/g, from about 0.2 cm³/g to about 0.9cm³/g, from about 0.2 cm³/g to about 0.8 cm³/g, from about 0.2 cm³/g toabout 0.7 cm³/g, from about 0.2 cm³/g to about 0.6 cm³/g, from about 0.2cm³/g to about 0.5 cm³/g, from about 0.3 cm³/g to about 1 cm³/g, fromabout 0.3 cm³/g to about 0.9 cm³/g, from about 0.3 cm³/g to about 0.8cm³/g, from about 0.3 cm³/g to about 0.7 cm³/g, from about 0.3 cm³/g toabout 0.6 cm³/g, or from about 0.3 cm³/g to about 0.5 cm3/g.

Embodiment B10 is the shaped porous carbon product of any one ofembodiments B1 to B9 wherein at least about 35%, at least about 40%, atleast about 45%, or at least about 50% of the pore volume of the shapedporous carbon product, as measured by the BJH process on the basis ofpores having a diameter from 1.7 nm to 100 nm, is attributable to poreshaving a mean pore diameter of from about 10 nm to about 50 nm.

Embodiment B11 is the shaped porous carbon product of any one ofembodiments B1 to B9 wherein from about 35% to about 80%, from about 35%to about 75%, from about 35% to about 65%, from about 40% to about 80%,from about 40% to about 75%, or from about 40% to about 70% of the porevolume of the shaped porous carbon product, as measured by the BJHprocess on the basis of pores having a diameter from 1.7 nm to 100 nm,is attributable to pores having a mean pore diameter of from about 10 nmto about 50 nm.

Embodiment B12 is the shaped porous carbon product of any one ofembodiments B1 to B11 wherein at least about 50%, at least about 60%, atleast about 70%, at least about 80%, or at least about 90% of the porevolume of the shaped porous carbon product, as measured by the BJHprocess on the basis of pores having a diameter from 1.7 nm to 100 nm,is attributable to pores having a mean pore diameter of from about 10 nmto about 100 nm.

Embodiment B13 is the shaped porous carbon product of any one ofembodiments B1 to B11 wherein from about 50% to about 95%, from about50% to about 90%, from about 50% to about 80%, from about 60% to about95%, from about 60% to about 90%, from about 60% to about 80%, fromabout 70% to about 95%, from about 70% to about 90%, from about 70% toabout 80%, from about 80% to about 95%, or from about 80% to about 90%of the pore volume of the shaped porous carbon product, as measured bythe BJH process on the basis of pores having a diameter from 1.7 nm to100 nm, is attributable to pores having a mean pore diameter of fromabout 10 nm to about 100 nm.

Embodiment B14 is the shaped porous carbon product of any one ofembodiments B1 to B13 wherein no more than about 10%, no more than about5%, or no more than about 1% of the pore volume of the shaped porouscarbon product, as measured by the BJH process on the basis of poreshaving a diameter from 1.7 nm to 100 nm, is attributable to pores havinga mean pore diameter less than 3 nm.

Embodiment B15 is the shaped porous carbon product of any one ofembodiments B1 to B 13 wherein from about 0.1% to about 10%, from about0.1% to about 5%, from about 0.1% to about 1%, from about 1% to about10%, or from about 1% to about 5% of the pore volume of the shapedporous carbon product, as measured by the BJH process on the basis ofpores having a diameter from 1.7 nm to 100 nm, is attributable to poreshaving a mean pore diameter less than 3 nm.

Embodiment B16 is the shaped porous carbon product of any one ofembodiments B1 to B15 wherein the shaped porous carbon product has apore size distribution such that the peak of the distribution is at adiameter greater than about 5 nm, greater than about 7.5 nm, greaterthan about 10 nm, greater than about 12.5 nm, greater than about 15 nm,or greater than about 20 nm.

Embodiment B17 is the shaped porous carbon product of any one ofembodiments B1 to B15 wherein the shaped porous carbon product has apore size distribution such that the peak of the distribution is at adiameter less than about 100 nm, less than about 90 nm, less than about80 nm, or less than about 70 nm.

Embodiment B18 is the shaped porous carbon product of any one ofembodiments B1 to B17 wherein the shaped porous carbon product has aradial piece crush strength from about 4.4 N/mm (1 lb/mm) to about 88N/mm (20 lbs/mm), from about 4.4 N/mm (1 lb/mm) to about 66 N/mm (15lbs/mm), from about 8.8 N/mm (2 lb/mm) to about 44 N/mm (10 lbs/mm),from about 15 N/mm (3.4 lbs/mm) to about 88 N/mm (20 lbs/mm), from about15 N/mm (3.4 lbs/mm) to about 44 N/mm (10 lbs/mm), from about 17 N/mm(3.8 lbs/mm) to about 88 N/mm (20 lbs/mm), from about 17 N/mm (3.8lbs/mm) to about 44 N/mm (10 lbs/mm), from about 20 N/mm (4.5 lbs/mm) toabout 88 N/mm (20 lbs/mm), or from about 20 N/mm (4.5 lbs/mm) to about44 N/mm (10 lbs/mm).

Embodiment B19 is the shaped porous carbon product of any one ofembodiments B1 to B18 wherein the shaped porous carbon product has amechanical piece crush strength greater than about 22 N (5 lbs), greaterthan about 36 N (8 lbs), or greater than about 44 N (10 lbs).

Embodiment B20 is the shaped porous carbon product of any one ofembodiments B1 to B18 wherein the shaped porous carbon product has amechanical piece crush strength from about 22 N (5 lbs) to about 88 N(20 lbs), from about 22 N (5 lbs) to about 66 N (15 lbs), or from about33 N (7.5 lbs) to about 66 N (15 lbs).

Embodiment B21 is the shaped porous carbon product of any one ofembodiments B1 to B20 wherein the shaped porous carbon product has amean diameter of at least about 50 μm, at least about 500 μm, at leastabout 1,000 μm, or at least about 10,000

Embodiment B22 is the shaped porous carbon product of any one ofembodiments B1 to B21 wherein the shaped porous carbon product has acarbonaceous material content of at least about 35 wt. %, at least about40 wt. %, at least about 45 wt. %, at least about 50 wt. %, at leastabout 55 wt. %, at least about 60 wt. %, at least about 65 wt. %, or atleast about 70 wt. %.

Embodiment B23 is the shaped porous carbon product of any one ofembodiments B1 to B21 wherein the shaped porous carbon product has acarbonaceous material content from about 35 wt. % to about 80 wt. %,from about 35 wt. % to about 75 wt. %, from about 40 wt. % to about 80wt. %, or from about 40 wt. % to about 75 wt. %.

Embodiment B24 is the shaped porous carbon product of any one ofembodiments B1 to B23 wherein the shaped porous carbon product has acarbonized binder content from about 10 wt. % to about 50 wt. %, fromabout 20 wt. % to about 50 wt. %, from about 25 wt. % to about 40 wt. %,or from about 25 wt. % to about 35 wt. %.

Embodiment C1 is a shaped porous carbon product prepared by a processaccording to any one of embodiments A1 to A81.

Embodiment D1 is a process of preparing a catalyst composition, theprocess comprising preparing a shaped porous carbon product according tothe process of any one of embodiments A1 to A81 and depositing acatalytically active component or precursor thereof on the shaped porouscarbon product.

Embodiment D2 is a process of preparing a catalyst composition, theprocess comprising depositing a catalytically active component orprecursor thereof on the shaped porous carbon product of any one ofembodiments B1 to B24.

Embodiment D3 is the process of embodiment D1 or D2 wherein thecatalytically active component or precursor thereof comprises a metal.

Embodiment D4 is the process of embodiment D3 wherein the metalcomprises at least one d-block metal.

Embodiment D5 is the process of embodiment D3 wherein the metalcomprises at least one metal selected from groups VI, V, VI, VII, VIII,IX, X, XI, XII, and XIII.

Embodiment D6 is the process of embodiment D3 wherein the metalcomprises a noble metal.

Embodiment D7 is the process of embodiment D3 wherein the metalcomprises a non-noble metal.

Embodiment D8 is the process of embodiment D3 wherein the metal isselected from the group consisting of cobalt, nickel, copper, zinc,iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium,rhenium, palladium, silver, osmium, iridium, platinum, gold, andcombinations thereof.

Embodiment D9 is the process of any one of embodiments D3 to D8 whereinthe metal constitutes from about 0.1% to about 50%, from about 0.1% toabout 25%, from about 0.1% to about 10%, from about 0.1% to about 5%,from about 0.25% to about 50%, from about 0.25% to about 25%, from about0.25% to about 10%, from about 0.25% to about 5%, from about 1% to about50%, from about 1% to about 25%, from about 1% to about 10%, from about1% to about 5%, from about 5% to about 50%, from about 5% to about 25%,or from about 5% to about 10% of the total weight of the catalystcomposition.

Embodiment E1 is a catalyst composition comprising a shaped porouscarbon product as a catalyst support and a catalytically activecomponent or precursor thereof, wherein, the shaped porous carbonproduct is prepared in accordance with any one of embodiments A1 to A81.

Embodiment E2 is a catalyst composition comprising a shaped porouscarbon product of any one of embodiments B1 to B24 as a catalyst supportand a catalytically active component or precursor thereof.

Embodiment E3 is the process of embodiment E1 or E2 wherein thecatalytically active component or precursor thereof comprises a metal.

Embodiment E4 is the process of embodiment E3 wherein the metalcomprises at least one d-block metal.

Embodiment E5 is the process of embodiment E3 wherein the metalcomprises at least one metal selected from groups VI, V, VI, VII, VIII,IX, X, XI, XII, and XIII.

Embodiment E6 is the process of embodiment E3 wherein the metalcomprises a noble metal.

Embodiment E7 is the process of embodiment E3 wherein the metalcomprises a non-noble metal.

Embodiment E8 is the process of embodiment E3 wherein the metal isselected from the group consisting of cobalt, nickel, copper, zinc,iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium,rhenium, palladium, silver, osmium, iridium, platinum, gold, andcombinations thereof.

Embodiment E9 is the process of any one of embodiments E3 to E8 whereinthe metal constitutes from about 0.1% to about 50%, from about 0.1% toabout 25%, from about 0.1% to about 10%, from about 0.1% to about 5%,from about 0.25% to about 50%, from about 0.25% to about 25%, from about0.25% to about 10%, from about 0.25% to about 5%, from about 1% to about50%, from about 1% to about 25%, from about 1% to about 10%, from about1% to about 5%, from about 5% to about 50%, from about 5% to about 25%,or from about 5% to about 10% of the total weight of the catalystcomposition.

The following non-limiting examples are provided to further illustratethe present invention.

EXAMPLES

Surface areas were determined from nitrogen adsorption data using theBET method as described in S. Brunauer, P. H. Emmett, E. Teller, J. Am.Chem. Soc. 1938, 60, 309-331, and ASTM D3663-03(2008) Standard TestMethod for Surface Area of Catalysts and Catalyst Carriers. Mean porediameters and pore volumes were determined in accordance with theprocedures described in E. P. Barrett, L. G. Joyner, P. P. Halenda, J.Am. Chem. Soc. 1951, 73, 373-380, and ASTM D4222-03(2008) Standard TestMethod for Determination of Nitrogen Adsorption and Desorption Isothermsof Catalysts and Catalyst Carriers by Static Volumetric Measurements.

Mercury Porosimetry measurements were conducted using an AutoPore VMercury Porosimeter from Micromeritics Instrument Corporation. Asuitable amount of carbon extrudates were loaded into an appropriatepenetrometer and mercury intrusion was measured in two sequentialstages: low pressure analysis (0 to 50 psia) followed by high pressureanalysis (50 to 33,000 psia). A total of 712 data points were collectedacross the whole range of pressure with a contact angle of 154.0°.

Radial piece crush strength measurements were conducted according toASTM D6175-03(2013) Standard Test Method for Radial Crush Strength ofExtruded Catalyst and Catalyst Carrier Particles using a press apparatusequipped with a Dillon GS100 Digital Force Gauge. Mean radial piececrush strength is the average value of independent measurements of atleast 10 different extrudate pellets.

Single piece crush strength were conducted according to ASTMD4179-03(2013) Standard Test Method for Single Pellet Crush Strength ofFormed Catalysts and Catalyst Carriers using a press apparatus equippedwith a Dillon GS100 Digital Force Gauge. Single piece crush strength isthe average value of independent measurements of at least 10 differentextrudate pellets.

Example 1 Preparation of Carbon Black Extrudates

36.4 g of carbon black powder (Cabot VULCAN XC72, 224 m²/g) was added inmultiple portions to a heated (overnight at 80° C.) aqueous solution(136.5 g) containing 24.3 wt. % Cerelose Dextrose from Ingredion and 4.7wt. % hydroxyethylcellulose from Sigma-Aldrich (SKU 54290, viscosity80-125 mPa·s (cP), 2% in H₂O (20° C.)). The mixture was stirred wellusing a spatula to produce a paste. This paste was loaded into a syringeand the material was extrudated into spaghetti-like strings with about1.5 mm diameter. After drying in a 70° C. oven for 5 hours under a dryair purge, these strings were cut into small pieces about 1.0 cm long.Then they were treated at 350° C. for 2 hours with 10° C./mintemperature ramp rate under continuous N₂ flow to carbonize the binderand produce a carbon black extrudate.

The properties of the resultant extrudate are show in Table 1.

TABLE 1 BET Surface Mean Pore Pore Volume Area (m²/g) Diameter (Å)(cm³/g) Extrudate of 110 110 0.15 Cabot VULCAN XC72

Example 2 Characterization of Component Carbon Black Powder

The properties of various carbon black powders utilized in the shapedporous carbon black products were characterized.

A. Physical Properties of Carbon Black Powders

The BET specific surface area, specific mean pore diameter and specificpore volume of these carbon black powder starting materials weredetermined using the methods described above, and are provided in Table2.

TABLE 2 BET Surface Mean Pore Pore Area Diameter Volume Carbon Black(m²/g) (Å) (cm³/g) Asbury 5365R 34 143 0.11 Asbury 5353R 35 186 0.14Asbury 5345R 35 207 0.11 Timcal ENSACO 64 140 0.24 250G Asbury 5348R 65220 0.31 Asbury 5358R 67 213 0.34 Asbury 5346R 80 145 0.28 Cabot MONARCH102 138 0.30 570 Orion HP 160 158 208 0.87 Cabot MONARCH 181 121 0.38700 Cabot VULCAN 224 161 0.43 XC72

B. Catalytic Performance

The carbon black powders were evaluated as catalyst support material inan oxidation reaction for converting glucose to glucaric acid asdescribed below.

(i) Oxidation of Glucose to Glucaric Acid (Protocol 1)

Suitably concentrated aqueous solutions of Me₄NAuO₂ and PtO(NO₃) wereadded together to carbon black powders by incipient wetness impregnationand agitated to impregnate the supports. The samples were dried in anoven at 70° C. overnight, and reduced at 350° C. under a forming gas (5%H₂ and 95% N₂) atmosphere for 4 hours with 2° C./min temperature ramprate to produce catalysts with a composition of 2.0 wt. % Au and 2.0 wt.% Pt. By using other carbon black supports, Au and Pt precursors, andadjusting amount of Au and Pt in solution, different catalysts withvarious Au and Pt loadings on a variety of commercial carbon blackpowders or particles from extrudates were prepared in a similar manner.

These catalysts were tested for glucose oxidation using the followingtesting protocol. Catalyst (8 mg) was weighed into a glass vial insertfollowed by addition of an aqueous glucose solution (250 μl of 0.55 M).The glass vial insert was loaded into a reactor and the reactor wasclosed. The atmosphere in the reactor was replaced with oxygen andpressurized to 618 kPa (75 psig) at room temperature. Reactor was heatedto 110° C. and maintained at the respective temperature for 2 hourswhile vials were shaken. After that, shaking was stopped and reactor wascooled to 40° C. Pressure in the reactor was then slowly released. Theglass vial insert was removed from the reactor and centrifuged. Thesolution was diluted with deionized water and analyzed by ionchromatography to determine the yield of glucaric acid. Selectivity isdefined as 100%×(glucaric acid)/(sum of glucaric acid and alloff-pathway species). Off-pathway species that cannot be converted toglucaric acid include 2-ketogluconic acid, 3-ketogluconic acid,4-ketogluconic acid, 5-ketogluconic acid, trihydroxyglutaric acid,tartaric acid, tartronic acid and oxalic acid. On-pathway speciesinclude glucose, gluconic acid, guluronic acid and glucuronic acid.On-pathway species are not used in the selectivity calculation becausethese intermediates can be partially converted to glucaric acid and arenot considered off-pathway. Results are presented in Table 3.

TABLE 3 Glucaric Surface Mean Pore Pore Acid Selec- Area Diameter VolumeYield tivity Support (m²/g) (Å) (cm³/g) (%) (%) Asbury 5302 211 99 0.2933 76 Asbury 5303 219 79 0.23 38 77 Asbury 5368 303 102 0.54 34 78Asbury 5379 271 163 0.83 33 75

(ii) Oxidation of Glucose to Glucaric Acid (Protocol 2)

Suitably concentrated aqueous solutions of K₂Pt(OH)₆ and CsAuO₂ wereadded together to carbon black powders by incipient wetness impregnationand agitated to impregnate the supports. The samples were dried in anoven at 40° C. overnight, and reduced at 250° C. under a forming gas (5%H₂ and 95% N₂) atmosphere for 3 hours with 5° C./min temperature ramprate. The final catalysts were washed with deionized water and finallydried at 40° C. to produce catalysts with a composition of 2.44 wt. % Ptand 2.38 wt. % Au. By using other carbon black supports, Au and Ptprecursors, and adjusting amount of Au and Pt in solution, differentcatalysts with various Au and Pt loadings on a variety of commercialcarbon black powders or particles from extrudates were prepared in asimilar manner.

These catalysts were tested for glucose oxidation using the followingtesting protocol. Catalyst (10 mg) was weighed into a glass vial insertfollowed by addition of an aqueous glucose solution (250 μl of 0.55 M).The glass vial insert was loaded into a reactor and the reactor wasclosed. The atmosphere in the reactor was replaced with oxygen andpressurized to 618 kPa (75 psig) at room temperature. Reactor was heatedto 90° C. and maintained at the respective temperature for 5 hours whilevials were shaken. After that, shaking was stopped and reactor wascooled to 40° C. Pressure in the reactor was then slowly released. Theglass vial insert was removed from the reactor and centrifuged. Thesolution was diluted with deionized water and analyzed by ionchromatography to determine the yield of glucaric acid and theselectivity as defined herein. Results are presented in Table 4.

TABLE 4 Glucaric Surface Mean Pore Pore Acid Selec- Area Diameter VolumeYield tivity Support (m²/g) (Å) (cm³/g) (%) (%) Asbury 5365R 34 143 0.1142 78 Asbury 5353R 35 186 0.14 38 82 Asbury 5345R 35 207 0.11 44 76Timcal ENSACO 64 140 0.24 60 83 250G Asbury 5348R 65 220 0.31 54 78Asbury 5358R 67 213 0.34 52 77 Asbury 5346R 80 145 0.28 48 75 CabotMONARCH 102 138 0.3 37 75 570 Orion HP 160 158 208 0.87 35 77 CabotMONARCH 181 121 0.38 42 77 700 Cabot VULCAN 224 161 0.43 46 77 XC72

Example 3 Preparation of Shaped Porous Carbon Black Product Using aVariety of Carbon Black Powders and Binders

By using other carbon black powders and carbohydrate binders, differentcarbon black extrudates were prepared as described in Example 1. Othercarbon black powders included, but were not limited to, Orion carbonHI-BLACK 40B2, Orion HI-BLACK 50LB, Orion Hi-BLACK SOL, Orion HP-160,Orion Carbon HI-BLACK N330, Timcal ENSACO 150 G, Timcal ENSACO 250 G,Timcal ENSACO 260G, Timcal ENSACO 250P, Cabot VULCAN XC72R, CabotMONARCH 120, Cabot MONARCH 280, Cabot MONARCH 570, Cabot MONARCH 700,Asbury 5365R, Asbury 5353R, Asbury 5345R, Asbury 5352, Asbury 5374,Asbury 5348R, Asbury 5358R, Sid Richardson SC159, Sid Richardson SR155.Other carbohydrate binders included, but were not limited to, CargillClearbrew 60/44 IX (80% Carbohydrate), Casco Lab Fructose 90 (70%Carbohydrate) and Molasses (80% Carbohydrate). Formulations with thesevariations yielded illustrative examples of the shaped carbon product ofthe present invention. The properties of some of these embodiments aredescribed in more detail below.

Example 4 Crush Testing of Carbon Black Extrudates

Extrudate pellets (Nos. 1-8 below), having an approximately 1.5 mmdiameter, were prepared according to the method described in Example 1except that the final pyrolysis times and temperatures were varied aslisted in Table 5 in the extrudate description column. After thepyrolysis step the extrudates were cut to the sizes ranging from 2-6 mmin length. The percentage of carbonized binder (after pyrolysis) presentin the shaped carbon product was determined by mass balance [i.e.,[(Weight_(Shaped Carbon Product)−Weight_(Carbon Black (in formulation))/Weight_(Shaped Carbon Product))×100].Total binder content after pyrolysis (i.e., total carbonized binder)varied from 15-50 wt. %.

Additional extrudate pellets (Nos. 9-11 below) were prepared accordinglyto the following procedure. Approximately 24.0 g of carbon black powder(Timcal ENSACO 250G, 65 m²/g) was added in multiple portions to anaqueous solution (100.0 g) containing 25.0 wt. % Cerelose Dextrose fromIngredion. The mixture was stirred well using a spatula to produce apaste. This paste was loaded into a syringe and the material wasextrudated into spaghetti-like strings with a 1.5 mm diameter. Afterdrying in a 100° C. oven for 3 hours under a dry air purge, thesestrings were cut into smaller pieces (2-6 mm lengths). Then they weretreated at one of the following conditions to produce carbon blackextrudates: (1) 250° C. for 3 hours with 10° C./min temperature ramprate under continuous N₂ flow; (2) 800° C. for 4 hours with 10° C./mintemperature ramp rate under continuous N₂ flow; (3) 200° C. for 3 hourswith 10° C./min temperature ramp rate in air. Binder content varied from15 to 50 wt. %. Table 5 presents the crush strength data for theextrudates prepared.

TABLE 5 Mean Mechan- Mean Mean ical Radial Radial Carbon- Piece PiecePiece ized Crush Crush Crush Binder Strength Strength Strength ContentNo. Extrudate Description (lb) (N/mm) (lb/mm) (wt. %) 1 Cabot MONARCH120 8.7 9.2 2.1 15 (Glucose + Hydroxyethylcellulose binder, 350° C./2h/N₂) 2 Cabot MONARCH 280 5.4 7.7 1.7 23 (Glucose +Hydroxyethylcellulose binder, 800° C./2 h/N₂) 3 Cabot MONARCH 700 12.312.3 2.8 31 (Glucose + Hydroxyethylcellulose binder, 350° C./2 h/N₂) 4Cabot MONARCH 700 6.3 6.3 1.4 34 (Glucose + Hydroxyethylcellulosebinder, 500° C./2 h/N₂) 5 Cabot MONARCH 700 18.7 18.5 4.2 31 (Glucose +Hydroxyethylcellulose binder, 800° C./2 h/N₂) 6 Cabot VULCAN XC72 5.65.6 1.2 30 (Glucose + Hydroxyethylcellulose binder, 800° C./2 h/N₂) 7Cabot VULCAN XC72R 7.8 7.8 1.8 38 (Glucose + Hydroxyethylcellulosebinder, 350° C./2 h/N₂) 8 Timcal ENSACO 250P 8.6 8.6 1.9 50 (Glucose +Hydroxyethylcellulose binder, 350° C./2 h/N₂) 9 Timcal ENSACO 250G 10.910.9 2.5 32 (Glucose binder, 800° C./4 h/N₂) 10 Timcal ENSACO 250G 6.26.2 1.4 29 (Glucose binder, 200° C./3 h/Air) 11 Timcal ENSACO 250G 3.83.8 0.9 29 (Glucose binder, 250° C./3 h/N₂)

Example 5 Preparation of Catalyst Compositions

The Cabot VULCAN XC72 carbon black extrudates prepared in Example 1 werefurther cut into small pieces of about 0.5 cm long for testing. Anaqueous solution (13 ml) containing 0.17 g Au in the form of Me₄NAuO₂and 0.26 g Pt in the form of PtO(NO₃) was mixed with 21.5 g of theseextrudates. The mixture was agitated to impregnate the carbon blacksupport and was dried in a 60° C. oven overnight under a dry air purge.The sample was then reduced at 350° C. under forming gas (5% H₂ and 95%N₂) atmosphere for 4 hours with 2° C./min temperature ramp rate. Thefinal catalyst was composed of about 0.80 wt. % Au and 1.2 wt. % Pt.

By using other carbon black extrudates prepared from the methoddescribed above, a series of Pt—Au extrudate catalysts spanning rangesin Au and Pt loadings, Pt/Au ratios and metal distributions (e.g.,eggshell, uniform, subsurface bands) could be prepared.

The cross section of a sample of the catalyst extrudate prepared withCabot VULCAN XC72 carbon black was analyzed using scanning electronmicroscopy. FIG. 1 provides an image of this analysis. The image showsthat platinum and gold metal was deposited on the external surface ofthe carbon black extrudate forming a shell coating the outer surfacesthe carbon black extrudate. FIG. 2 provides a magnified view of one ofcatalyst extrudate cross-sections with measurements of the diameter ofthe carbon black extrudate (i.e., 1.14 mm) and thickness of the platinumand gold shell (average of about 100 μm) on the carbon black extrudateouter surface.

Example 6 Testing of Au/Pt Carbon Black Extrudate Catalysts (using CabotMONARCH 700) in a Fixed-Bed Reactor for the Oxidation of Glucose toGlucaric Acid

Extrudates based on carbon black Cabot MONARCH 700 with glucose andhydroxyethylcellulose binder and subsequent catalyst with 0.80 wt. % Auand 1.20 wt. % Pt were prepared by mixing carbon black Cabot MONARCH 700(42.0 g) and a binder solution (145.8 g prepared by heating a solutioncontaining 3.4 wt. % hydroxyethylcellulose and 28.6 wt. % glucose at 80°C. overnight)), The resultant paste was loaded into a syringe and thematerial was extrudated into spaghetti-like strings with a 1.5 mmdiameter. After drying in a 100° C. oven for 3 hours under a dry airpurge, these strings were cut into smaller pieces (2-6 mm lengths) andpyrolyzed at 350° C. for 2 hours under a nitrogen atmosphere. The finalcarbonized binder content in carbon extrudates was 31 wt. %. Thecatalyst was then prepared using the method described in Example 5.Oxidation of glucose reactions were conducted in a 12.7 mm (0.5-inch) ODby 83 cm long 316 stainless steel tube with co-current down-flow of gasand liquid. Catalyst beds were vibration packed with 1.0 mm glass beadsat the top to approximately 8 cm depth, followed by catalyst (67 cm beddepth containing 20.0 g, 0.80 wt. % Au+1.2wt. % Pt on Cabot MONARCH 700carbon black pellets with a length of 0.5 cm and diameter of 1.5 mmprepared using the method described in Example 3), then 1.0 mm glassbeads at the bottom to approximately 8 cm depth. Quartz wool plugsseparated the catalyst bed from the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 6.The catalyst was tested for approximately 350 hours of time on stream(TOS).

Table 6 describes the fixed bed reactor conditions and resultantextrudate catalyst performance. The catalyst productivity in Table 6 is35 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.70 gram (glucaricacid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 6 Reactor Gas block Glucose feed Reactor Liquid flowrate/temperature/ concentration/ pressure/ flowrate/ mL min⁻¹ GlucoseGlucaric ° C. wt. % psi mL min⁻¹ (STP) conversion/% acid yield/%Selectivity/% 130 20 750 2.00 768 >99 50 86

BET surface area measurements and BJM pore volume distributionmeasurements were made on the following carbon black and extrudatesamples:

Sample 1: MONARCH 700 carbon black material.

Sample 2: Fresh MONARCH 700 extrudate prepared in accordance with thisExample.

Sample 3: MONARCH 700 extrudate of Example 4 following 350 hours onstream in a fixed bed reactor (described in Example 6).

Sample 4: An aqueous solution (915.0 g) containing 4.0 wt. %hydroxyethylcellulose (Sigma-Aldrich, SKU 54290, viscosity 80-125 mPa·s(cP), 2% in H₂O (20° C.)) and 56.0 wt. % glucose (ADM Corn Processing,Dextrose Monohydrate 99.7DE with 91.2255 wt. % Glucose content) wasprepared by stirring 36.6 g hydroxyethylcellulose and 561.7 g DextroseMonohydrate in 316.7 ml D.I. water at 80° C. for 16 hours. After coolingto ambient temperature, this viscous solution was added to 400.0 gcarbon black powder (Cabot MONARCH 700) in a blender/kneader and thematerial was mixed/kneaded for 1 hour. The material was then loaded intoa 2.54 cm (1-inch) Bonnot BB Gun Extruder and extrudated into spaghettilike strings with ca. 1.5 mm diameter at cross section. These stringswere dried under a dry air purge in a 120° C. oven for 16 hours and thenpyrolyzed at 800° C. for 2 hours with 5° C./min ramp rate under anitrogen purge. The final carbonized binder content was to be 36 wt. %.

Sample 5: Prepared as described by Example 9.

Sample 6: Prepared as described by Example 12.

Sample 7: An aqueous solution (166.0 g) containing 4.0 wt. %hydroxyethylcellulose (Sigma-Aldrich, SKU 54290, viscosity 80-125 mPa·s(cP), 2% in H₂O (20° C.)) and 56.0 wt. % glucose (ADM Corn Processing,Dextrose Monohydrate 99.7DE with 91.2255 wt. % Glucose content) wasprepared by stirring 6.64 g hydroxyethylcellulose and 84.8 g DextroseMonohydrate in 74.6 ml D.I. water at 80° C. for 16 hours. After coolingto ambient temperature, this viscous solution was added to 60.0 g carbonpowder (Asbury 5368) in a blender/kneader and the material wasmixed/kneaded for 1 hour. The material was then loaded into a 2.54 cm (1inch) Bonnot BB Gun Extruder and extrudated into spaghetti like stringswith ca. 1.5 mm diameter at cross section. These strings were driedunder a dry air purge in a 120° C. oven for 16 hours and then pyrolyzedat 800° C. for 2 hours with 5° C./min ramp rate under a nitrogen purge.The final carbonized binder content was 40 wt. %.

Sample 8: Commercially available activated carbon extrudate Sud ChemieG32H-N-75.

Sample 9: Commercially available activated carbon extrudate DonauSupersorbon K4-35.

The results are presented in Table 7.

TABLE 7 Pores Pores Pores between between 10 BET Mean BJH <3 nm 10 and50 nm and 100 nm Carbonized Surface Pore Pore (% of (% of (% of BJHBinder Area Diameter Volume BJH pore BJH pore pore Content Sample (m²/g)(nm) (cm³/g) volume) volume) volume) (wt %) Sample 1 180 12 0.38 5 40 75 0 Sample 2 178 11 0.29 7 45 75 36 Sample 3 98 18 0.31 3 50 90 36 Sample4 182 13 0.36 4 55 80 36 Sample 5 194 11 0.29 6 45 75 36 Sample 5 234 100.29 7 45 70 36 Sample 6 218 12 0.33 5 60 80 40 Sample 8 1164 3.4 0.6340 <15 15 ** Sample 9 1019 2.7 0.31 65 5 7 **

FIG. 3 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for a raw MONARCH 700 carbon black material. FIG. 4presents a plot of the cumulative pore volume (%) as a function of porediameter for a fresh catalyst prepared from a carbon black extrudateusing MONARCH 700 and a glucose/hydroxyethylcellulose binder. FIG. 5presents a plot of the cumulative pore volume (%) as a function of porediameter for the catalyst extrudate of FIG. 2 following 350 hours of usein a fixed bed reactor for the oxidation of glucose to glucaric acid.FIG. 6 presents a plot of the cumulative pore volume (%) as a functionof pore diameter for an extrudate using MONARCH 700 carbon black and aglucose/hydroxyethyl cellulose binder. FIG. 7 presents a plot of thecumulative pore volume (%) as a function of pore diameter for anextrudate using Sid Richardson SC 159 carbon black and aglucose/hydroxyethyl cellulose binder. FIG. 8 presents a plot of thecumulative pore volume (%) as a function of pore diameter for anextrudate using Sid Richardson SC 159 carbon black and aglucose/hydroxyethyl cellulose binder prepared in accordance withExample 12. FIG. 9 presents a plot of the cumulative pore volume (%) asa function of pore diameter for an extrudate using Asbury 5368 carbonblack and a glucose/hydroxyethyl cellulose binder. FIG. 10 presents aplot of the cumulative pore volume (%) as a function of pore diameterfor a commercially available activated carbon extrudate of Sud ChemieG32H-N-75. FIG. 11 presents a plot of the cumulative pore volume (%) asa function of pore diameter for a commercially available activatedcarbon extrudate of Donau Supersorbon K4-35.

FIG. 12 presents the pore size distribution for an extrudate using SidRichardson SC159 carbon black and a glucose/hydroxyethyl cellulosebinder measured by mercury porosimetry. These plots show that themicropore contribution to pore volume for carbon black extrudatecatalysts (fresh and after use) is very low. In particular the plotsshow that the micropore contribution (pores <3 nm) is less than 10% ofthe BJH pore volume. In some instances the micropore contribution (pores<3 nm) is less than 6% of the BJH pore volume, and in some instances themicropore contribution (pores <3 nm) is less than 4% of the BJH porevolume. In contrast, the micropore contribution to pore volume for anactivated carbon extrudate catalyst is exceedingly high at 40%. Also,the plots show that the contribution to pore volume from pores having amean diameter from about 10 nm to 50 nm for the carbon black catalystswas about 40% or higher. On the other hand, the contribution to porevolume from pores having a mean diameter from about 10 nm to 50 nm forthe activated carbon catalyst was less than 15%. The plots show that thecontribution to pore volume from pores having a mean diameter from about10 nm to 100 nm for the carbon black catalysts was about 70% or higher.On the other hand, the contribution to pore volume from pores having amean diameter from about 10 nm to 100 nm for the activated carboncatalyst was 15% or less.

Example 7 Testing of Au/Pt Carbon Black Extrudate Catalysts (using CabotVULCAN XC72) in a Fixed-Bed Reactor for the Oxidation of Glucose toGlucaric Acid

Extrudates based on carbon black Cabot VULCAN XC72 and subsequentcatalyst with 0.80 wt. % Au and 1.20 wt. % Pt were prepared by mixingcarbon black Cabot VULCAN XC72 (36.4 g) and a binder solution (136.5 gprepared by heating a solution containing 3.7 wt. %hydroxyethylcellulose and 24.4 wt. % glucose at 80° C. overnight). Theresultant paste was loaded into a syringe and the material wasextrudated into spaghetti-like strings with a 1.5 mm diameter followedby drying at 120° C. for 4 hours in air, and pyrolysis at 350° C. for 2hours under a nitrogen atmosphere. The final binder content in pyrolyzedcarbon extrudates was 30 wt. %. The catalysts were prepared using themethod described in Example 3. The catalyst was tested in the same 12.7mm (0.5-inch) OD fixed-bed reactor as in Example 6. Table 8 describesthe fixed bed reactor conditions and resultant extrudate catalystperformance. The catalyst productivity in Table 8 is 36 gram (glucaricacid) per gram (Pt+Au)⁻¹hr⁻¹ or 0.72 gram (glucaric acid) per gram(catalyst)⁻¹ hr⁻¹.

TABLE 8 Reactor Gas block Glucose feed Reactor Liquid flowrate/temperature/ concentration/ pressure/ flowrate/ mL min⁻¹ GlucoseGlucaric ° C. wt. % psi mL min⁻¹ (STP) conversion/% acid yield/%Selectivity/% 130 20 750 2.00 768 >99 52 87

Example 8 Oxidation of Glucose to Glucaric Acid-Activated Carbons withHigh Surface Areas (Comparative)

The same synthesis procedure described in Example 6 was used to preparePt—Au catalysts supported on high surface area activated carbon. Theactivated carbon extrudates were crushed and sieved to <90 μm prior tothe catalyst preparation and screening. The catalysts were screened inthe same reactor under the same conditions described in Example2(B)(ii). As shown in Table 9, the high surface area activated carboncarriers were found to exhibit lower activity and lower selectivity (asdefined herein).

TABLE 9 Glucaric Surface Mean Pore Pore Acid Selec- Area Diameter VolumeYield tivity Support (m²/g) (Å) (cm³/g) (%) (%) Donau Supersorbon 101927 0.31 22 66 K4-35 Donau Supersorbon 1050 39 0.71 18 68 SX30 Norit RX3Extra 1239 37 0.23 20 70

Example 9 Preparation of Carbon Black Extrudate Catalysts Attrition andAbrasion Testing

An aqueous solution (113 g) containing 4.0 wt. % hydroxyethylcellulose(Sigma-Aldrich, SKU 54290, viscosity 80-125 mPa·s (cP), 2% in H₂O (20°C.)) and 56.0 wt. % glucose (ADM Corn Processing, Dextrose Monohydrate99.7DE with 91.2255 wt. % Glucose content) was prepared by stirring 4.5g hydroxyethylcellulose and 69.4 g Dextrose Monohydrate in 39.1 ml D.I.water at 80° C. overnight. After cooling to room temperature, thisviscous solution was added to 50 g carbon black powder (Sid RichardsonSC159, 231 m²/g) in a blender/kneader and the material was mixed/kneadedfor 1 hour. The material was then loaded into a 2.54 cm (1 inch) BonnotBB Gun Extruder and extrudated into spaghetti like strings with ca. 1.5mm diameter at cross section. These strings were dried under a dry airpurge in a 120° C. oven overnight and then pyrolyzed at 800° C. for 4hours with 5° C./min ramp rate under a nitrogen purge. The extruded andpyrolyzed samples were cut into small pieces of about 0.5 cm long fortesting.

The properties of the resultant extrudate are show in Table 10. BET andcrush strength measurements performed as described in the currentdisclosure.

TABLE 10 BET Single Piece Mean Surface Mean Pore Pore Crush Radial PieceArea Diameter Volume Strength Crush Strength (m²/g) (Å) (cm³/g) (N)(N/mm) 194 112 0.29 90 30

Extrudates prepared in accordance with this example were tested for thedetermination of attrition index (ASTM D4058-96) and abrasion lossaccording to the procedure described below.

Measurement of Attrition Index.

The ASTM attrition index (ATTR) is a measurement of the resistance of acatalyst or extrudate particle to attrition wear, due to the repeatedstriking of the particle against hard surfaces within the specified testdrum. The diameter and length of the drum is similar to that describedin ASTM D4058, with a rolling apparatus capable of delivering 55 to 65RPM of rotation to the test drum. The percentage of the original samplethat remains on a 20-mesh sieve is called the “Percent Retained” resultof the test. The results of the test can be used, on a relative basis,as a measure of fines production during the handling, transportation,and use of the catalyst or extrudate material. A percent retained resultof >97% is desirable for an industrial application.

Approximately 100 g of the extrudate material prepared in Example 9above was transferred to the test drum which was fastened andtransferred to the rolling apparatus and rolled at 55 to 65 RPM for 35minutes. The weight percent retained after the test was 99.7%.

Measurement of Abrasion Loss.

The abrasion loss (ABL) is an alternate measurement of the resistance ofa catalyst or extrudate particle to wear, due to the intense horizontalagitation of the particles within the confines of a 30-mesh sieve. Theresults of this procedure can be used, on a relative basis, as a measureof fines production during the handling, transportation, and use of thecatalyst or adsorbent material. An abrasion loss of <2 wt. % is desiredfor an industrial application. Approximately 100 g of the extrudatematerial prepared in example 9 above was first de-dusted on a 20-meshsieve by gently moving the sieve side-to-side at least 20 times. Thede-dusted sample was then transferred to the inside of a clean, 30-meshsieve stacked above a clean sieve pan for the collection of fines. Thecomplete sieve stack was then assembled onto a RO-Tap RX-29 sieveshaker, covered securely and shaken for 30 minutes. The fines generatedwere weighed to provide a sample abrasion loss of 0.016 wt. %.

Example 10 Testing of Au/Pt Carbon Black Extrudate Catalysts of Example9 in a Fixed-Bed Reactor for the Oxidation of Glucose to Glucaric Acid

The carbon black extrudates prepared from the method described inExample 9 were further cut into small pieces of about 0.5 cm long fortesting. To 27.0 g of these extrudates, an aqueous solution (8.0 ml)containing 0.16 g Au in the form of Me₄NAuO₂ and 0.24 g Pt in the formof PtO(NO₃) was added. The mixture was agitated to impregnate the carbonblack support and was dried in a 70° C. oven for 1 hour under a dry airpurge. The sample was then reduced at 350° C. under forming gas (5% H₂and 95% N₂) atmosphere for 4 hours with 2° C./min temperature ramp rate.The final catalyst was composed of ca. 0.60 wt. % Au and 0.90 wt. % Pt.By using other carbon black extrudates prepared from the methodsdescribed herein, a series of Pt-Au extrudate catalysts spanning rangesin Au and Pt loadings, Pt/Au ratios and metal distributions (e.g.,eggshell, uniform, subsurface bands) can be prepared.

The glucose to glucaric acid oxidation reaction was conducted in a 1.27cm (½ inch) OD by 83 cm long 316 stainless steel tube with co-currentdown-flow of gas and liquid. Catalyst beds were vibration packed with1.0 mm glass beads at the top to approximately 10 cm depth, followed bycatalyst (63 cm bed depth containing 27.4 g, 0.60 wt. % Au+0.90 wt. % Pton Sid Richardson SC159 carbon black pellets with a length of 0.5 cm anddiameter of 1.4 mm prepared using the method described, then 1.0 mmglass beads at the bottom to approximately 10 cm depth. Quartz woolplugs separated the catalyst bed from the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 11.The catalyst was tested for ca. 920 hours on stream and showed stableperformance. Table 11 describes the fixed bed reactor conditions andresultant extrudate catalyst performance. The catalyst productivity inTable 11 is 23 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.35 gram(glucaric acid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 11 Gas Reactor block Glucose feed Reactor Liquid flowrate/temperature/ concentration/ pressure/ flowrate/ mL min⁻¹ GlucoseGlucaric ° C. wt. % psi mL min⁻¹ (STP) conversion/% acid yield/%Selectivity/ 125 20 750 2.00 512 >99 32 79

After 920 hours on stream the catalyst extrudate was removed andre-submitted for mechanical crush strength testing. The mean singlepiece crush strength and mean radial piece crush strength data werefound be within experimental error unchanged from the data listed inTable 10, thereby illustrating that the extrudate catalyst prepared bythe method described is productive, selective and stable under thecontinuous flow conditions described.

Example 11 Testing of Au/Pt Carbon Black Extrudate Catalysts (usingAsbury 5368) in a Fixed-Bed Reactor for the Oxidation of Glucose toGlucaric Acid

Reactions were conducted in a 1.27 cm (½ inch) OD by 83 cm long 316stainless steel tube with co-current down-flow of gas and liquid.Catalyst beds were vibration packed with 1.0 mm glass beads at the topto approximately 8 cm depth, followed by catalyst (73 cm bed depthcontaining 35.0 g, 0.50 wt. % Au+0.85 wt. % Pt on Asbury 5368 extrudedpellets (as previously described for Sample 7 (Example 6) with a lengthof 0.5 cm and diameter of 1.4 mm prepared using the method described inprevious example 9), then 1.0 mm glass beads at the bottom toapproximately 8 cm depth. Quartz wool plugs separated the catalyst bedfrom the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 12.The catalyst was tested for ca. 240 hours TOS and showed stableperformance. Table 12 describes the fixed bed reactor conditions andresultant extrudate catalyst performance. The catalyst productivity inTable 12 is 20 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.27 gram(glucaric acid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 12 0.50 wt. % Au + 0.85 wt. % Pt/Asbury 5368 Extrudate (stableperformance over 240 hours on stream) Gas Reactor block Glucose feedReactor Liquid flowrate/ temperature/ concentration/ pressure/ flowrate/mL min⁻¹ Glucose Glucaric ° C. wt. % psi mL min⁻¹ (STP) conversion/%acid yield/% Selectivity 125 20 750 2.00 512 >99 31 76

Example 12 Preparation of Carbon Black Extrudate Catalysts on PartiallyOxidized Support

Sid Richardson SC159 carbon black extrudates prepared from the methoddescribed in example 9 were oxidized in air at 300° C. for 3 hours with5° C./min ramp rate to give partially oxidized pellets. To 36.0 g ofthese partially oxidized extrudates, an aqueous solution (9.0 ml)containing 0.18 g Au in the form of Me4NAuO2 and 0.31 g Pt in the formof PtO(NO3) was added. The mixture was agitated to impregnate the carbonblack support and was dried in a 60° C. oven overnight under a dry airpurge. The sample was then reduced at 350° C. under forming gas (5% H2and 95% N2) atmosphere for 4 hours with 2° C./min temperature ramp rate.The final catalyst was composed of ca. 0.50 wt. % Au and 0.85 wt. % Pt.By using other carbon black extrudates prepared from the methoddescribed herein, a series of Pt—Au extrudate catalysts spanning rangesin Au and Pt loadings, Pt/Au ratios and metal distributions (e.g.,eggshell, uniform, subsurface bands) could be prepared. The glucose toglucaric acid oxidation reaction was conducted in a in a 1.27 cm (½inch) OD by 83 cm long 316 stainless steel tube with co-currentdown-flow of gas and liquid. Catalyst beds were vibration packed with1.0 mm glass beads at the top to approximately 6 cm depth, followed bycatalyst (70.4 cm bed depth containing 34.5 g, 0.50 wt. % Au+0.85 wt. %Pt on partially oxidized Sid Richardson SC159 carbon black pellets witha length of 0.5 cm and diameter of 1.5 mm prepared using the methoddescribed in Example 2), then 1.0 mm glass beads at the bottom toapproximately 6 cm depth. Quartz wool plugs separated the catalyst bedfrom the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed dry air) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. A backpressure regulator controlled reactor pressure as indicated in Table 13.The catalyst was tested for ca. 230 hours TOS and showed stableperformance. Table 13 describes the fixed bed reactor conditions andresultant extrudate catalyst performance. The catalyst productivity inTable 13 is 26 gram (glucaric acid) per gram (Pt+Au)⁻¹ hr⁻¹ or 0.36 gram(glucaric acid) per gram (catalyst)⁻¹ hr⁻¹.

TABLE 13 Gas Glucose feed Reactor Liquid flowrate/ Glucose GlucaricReactor block concentration/ pressure/ flowrate/ mL min⁻¹ conversion/acid yield/ temperature/° C. wt. % psi mL min⁻¹ (STP) % % 125 20 7502.00 512 >99 42

Example 13 Preparation of Carbon Black Extrudates using aPoly(vinylalcohol) Porogen

An aqueous solution (490.0 g) containing 8.0 wt. % Mowiol 8-88Poly(vinylalcohol) (Mw 67k, Sigma-Aldrich 81383) and 36.0 wt. % glucose(ADM Corn Processing, Dextrose Monohydrate 99.7DE with 91.2255 wt. %Glucose content) was prepared by stirring 39.2 g Mowiol 8-88Poly(vinylalcohol) and 193.4 g Dextrose Monohydrate in 257.4 ml D.I.water at 70° C. overnight. After cooling to room temperature, thissolution was added to 230 g carbon black powder (Sid Richardson SC159)in a blender/kneader and the material was mixed/kneaded for 1 hour. Thematerial was then loaded into a 2.54 cm (1 inch) Bonnot BB Gun Extruderand extrudated into spaghetti like strings with ca. 1.5 mm diameter atcross section. These strings were further dried in a 90° C. ovenovernight under a dry air purge and then pyrolyzed at 600° C. for 4hours with 5° C./min ramp rate in a nitrogen atmosphere. The finalcarbonized binder content was 24 wt. %. The resultant extrudate (3-5 mmin length) possessed a surface area of 149 m²/g, a pore volume of 0.35cm³/g and a mean pore diameter of 16 nm. The mean radial piece crushstrength of these pellets was measured to be 11.5 N/mm. The single piececrush strength was measured to be 42N.

Example 14 Testing of Au/Pt Activated Carbon Extrudate Catalysts (usingClariant Donau Supersorbon K4-35 Activated Carbon Extrudate) in aFixed-Bed Reactor for the Oxidation of Glucose to Glucaric Acid

Catalyst based on activated carbon Clariant Supersorbon K 4-35 wasprepared using the same method described in Example 7. Oxidation ofglucose reactions were conducted using the same method described inExample 2(B)(ii). A catalyst bed depth of 73 cm containing 27.0 g, 0.53wt. % Au+0.90 wt. % Pt on Clariant Supersorbon K 4-35 activated carbonpellets with a length of 0.5 cm and diameter of 1.4 mm was tested forapproximately 40 hours of time on stream (TOS). Table 14 describes thefixed bed reactor conditions and resultant extrudate catalystperformance. After 40 hours on stream the glucaric acid yield and thecatalyst productivity were determined to be lower than the shaped carbonblack catalysts of the invention.

TABLE 14 Gas Glucose feed Reactor Liquid flowrate/ Reactor blockconcentration/ pressure/ flowrate/ mL min⁻¹ temperature/° C. wt. % psimL min⁻¹ (STP) 125 20 750 2.00 512

Example 15 Preparation of Carbon Black Extrudates

An aqueous solution (915 g) containing 4.0 wt. % hydroxyethylcellulose(HEC) (Sigma-Aldrich, SKU 54290, viscosity 80-125 mPa·s (cP) at 2% inH₂O (20° C.)) and 56.0 wt. % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2 wt. % Glucose content) was prepared bystirring 36.6 g hydroxyethylcellulose and 561.7 g Dextrose Monohydratein 316.7 ml D.I. water at approximately 80° C. for 2 hours. To thisviscous solution was added 400.1 g of Sid Richardson SC159 carbon blackpowder, the mixture was then mixed for a further 10 minutes. Thematerial was then loaded into a 2.54 cm (1-inch) diameter Bonnot “BBGun” Catalyst Extruder, fitted with a 6.4 mm (0.25-inch) spacer and adie with 1.6 mm cylindrical holes, and extruded into spaghetti-likestrings. The extrudate was dried in a 110° C. oven overnight, thenpyrolyzed in a stationary lab furnace under a nitrogen purge at 800° C.for 4 hours (after ramping the temperature up at 5° C./minute to reachthe target temperature). The pyrolyzed extrudate was analyzed for BETspecific surface area, BJH specific pore volume, and bulk diameter, andradial piece crush strength. These results of these analyses areprovided in Table 15.

TABLE 15 Properties of the pyrolyzed extrudate from Example 15 N₂ BETBJH N₂ Diameter at Radial Piece Surface Area Pore Volume cross sectionCrush Strength (m²/g) (cm³/g) (mm) (N/mm) 207 0.30 1.5 17

Example 16 Preparation of Carbon Black Extrudates

An aqueous solution (3813 g) containing 4.0 wt. % hydroxyethylcellulose(HEC) (Sigma-Aldrich, SKU 54290, viscosity 80-125 mPa·s (cP) at 2% inH₂O (20° C.)) and 56.0 wt. % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2 wt. % Glucose content) was prepared bystirring 153 g hydroxyethylcellulose and 2340 g Dextrose Monohydrate in1320 ml D.I. water at approximately 80° C. for 3 hours. This viscoussolution was added over 3.5 minutes to 1670 g of Sid Richardson SC159carbon black powder in a 45.7 cm (18 inch) diameter Simpson mix-muller,the mixture was then mixed for a further 20 minutes in the mix-muller.The material was then loaded into a 5.7 cm (2.25-inch) diameter BonnotCatalyst Extruder, fitted with 5 dies with 26 cylindrical holes each 1.6mm ( 1/16-inch) internal diameter (JMP Industries, part number0388P062), and no spacer, and extruded into spaghetti-like strings. 1515g of the extrudate was dried in a 110° C. oven overnight, to produce1240 g of dried extrudate. The product was then pyrolyzed in astationary tube furnace under a nitrogen purge at 800° C. for 4 hours.The pyrolyzed extrudate was analyzed for BET specific surface area, BJHspecific pore volume, and bulk diameter, and radial piece crushstrength. These results of these analyses are provided in Table 16.

TABLE 16 Properties of the pyrolyzed extrudate from Example 16 N₂ BETBJH N₂ Diameter at Radial Piece Surface Area Pore Volume cross sectionCrush Strength (m²/g) (cm³/g) (mm) (N/mm) 169 0.23 1.4 13

Example 17 Preparation of Carbon Black Extrudates using Batch Pyrolysisin a Rotary Tube Furnace

An aqueous solution (3813 g) containing 4.0 wt. % of Dow Cellosize HECQP 40 hydroxyethylcellulose (viscosity 80-125 mPa·s (cP) at 2% in H₂O(20° C.)), and 56.0 wt. % glucose (ADM Corn Processing, DextroseMonohydrate 99.7DE with 91.2 wt. % Glucose content) was prepared bystirring 153 g hydroxyethylcellulose and 2340 g Dextrose Monohydrate in1320 ml D.I. water at approximately 80° C. for 3 hours. This viscoussolution was added over 3.5 minutes to 1670 g of Sid Richardson SC159carbon black powder in a 45.7 cm (18 inch) diameter Simpson mix-muller,the mixture was then mixed for a further 20 minutes in the mix-muller.The material was then loaded into a 5.7 cm (2.25-inch) diameter BonnotCatalyst Extruder, fitted with 5 dies with 26 cylindrical holes each 1.6mm ( 1/16-inch) internal diameter (JMP Industries, part number0388P062), and no spacer, and extruded into spaghetti-like strings. 3.9kg of the extrudate was dried in a 110° C. oven overnight, to produce2.93 kg of dried extrudate. This dried extrudate was then screened overan 18 mesh screen, and 2.91 kg of screened material were collected.

The mixing, extrusion, drying and screening procedure above was repeated3 more times to generate a total of 4 batches of dried, screenedextrudate, which were combined, as summarized in Table 17.

TABLE 17 Production of Carbon Black Extrudate in a 5.7 cm (2.25-inch)Extruder Mass of wet Mass of dried extrudate Mass of dried extrudateafter collected extrudate screening Sample number (kg) (kg) (kg) 17.13.90 2.93 2.91 17.2 4.66 3.80 3.76 17.3 5.17 4.24 4.20 17.4 4.85 3.743.71 Combined Total 18.58 14.71 14.58

Measurement of residual moisture on a moisture balance (using atemperature setting of 160° C. and a time of 30 minutes for a 5 gsample) indicated the dried extrudates had 17.7 wt. % moistureremaining.

650 g batches of the combined dried & screened extrudate of were thenpyrolyzed in a rotary tube furnace under a nitrogen purge at 800° C. for2 hours, each batch producing approximately 350 g of pyrolyzed product.For each batch, 650 g of the carbon black extrudates (prepared from SidRichardson SC159 with glucose and hydroxyethylcellulose binders) wereloaded into an MTI Corporation 12.7 cm (5-inch) Quartz Tube Three ZoneRotary Tube Furnace (OTF-1200X-5L-R-III-UL). The carbon black extrudateswere pyrolyzed with the 12.7 cm (5-inch) quartz tube rotating at 4.0 rpmunder a nitrogen atmosphere at 800° C. for 2 hours with the followingtemperature ramp: ambient temperature to 200° C. at 10° C./min, 200° C.to 600° C. at 5° C./min, 600° C. to 800° C. at 10° C./min, hold at 800°C. for 2 hours, then allowed to cool to ambient temperature, still undernitrogen purge. 350 g of pyrolyzed carbon black extrudates wererecovered, for a simple “as is” mass-based yield of 53.8% yield (350g/650 g).

Measurement of residual moisture on a moisture balance (using atemperature setting of 160° C. and a time of 30 minutes for a 5 gsample) indicated the batch-pyrolyzed extrudates had 2.3 wt. % moisture,giving a dry-basis yield of 342 g. Since the dried extrudate startingmaterial for the pyrolysis had a moisture level of 17.7 wt. %, the 650 grepresents 535 g on a dry basis, and thus the yield of the pyrolysis ona dry basis is 63.9% (342 g/535 g). On a dry basis the dried extrudatestarting material for the pyrolysis is 40 wt. % carbon black and 60 wt.% binder. Assuming the mass of carbon black is unchanged by thepyrolysis, then on a dry basis the pyrolyzed extrudates have a carbonblack content of 62.6 wt. % and a carbonized binder content of 37.4 wt.%.

The properties of the batch-pyrolyzed extrudate are shown in Table 18.Other carbon black extrudates can be pyrolyzed at various temperaturesin a similar manner, or using a continuously operating rotary kiln asdescribed in the following Example.

TABLE 18 Properties of Carbon Black Extrudate Batch- Pyrolyzed in aRotary Tube Furnace Radial Piece N₂ BET N₂ Mean BJH N₂ Crush SurfaceArea Pore Diameter Pore Volume Strength (m²/g) (Å) (cm³/g) (N/mm)Combined 191 100 0.29 15 Extrudates of Example 17 Batch- Pyrolyzed at800° C. for 2 hours

Example 18 Preparation of Carbon Black Extrudates using ContinuousPyrolysis in Rotary Kiln

The mixing, extrusion, drying, and screening procedure described inExample 17 was repeated 10 more times to generate an additional 33.4 kgof dried, screened extrudate, which were combined. 25.73 kg of thecombined dried & screened extrudate was then pyrolyzed in a continuousrotary kiln, with a continuous nitrogen purge (counter current flow vs.the extrudate), with a continuous feed of dried extrudate atapproximately 0.5 kg/hour, with product collected at a number of setpoint conditions summarized in Table 19. The rotary kiln waselectrically heated. The temperature set points for the external heatersare shown in Table 19, along with the calculated residence time of thematerial in the heating zone. The temperature and residence time wereadjusted to influence the surface area of the product. A total of 12.47kg of pyrolyzed product was collected, for a simple “as is” mass-basedyield of 48.5%.

Measurement of residual moisture on a moisture balance (using atemperature setting of 160° C. and a time of 30 minutes for a 5g sample)indicated the continuous-pyrolyzed extrudates had 2.3 wt. % moisture,giving a dry-basis yield of 12.18 kg. Since the dried extrudate startingmaterial for the pyrolysis had a moisture level of 17.7 wt. %, the 25.73kg represents 21.18 kg on a dry basis, and thus the yield of thepyrolysis on a dry basis is 57.5% (12.18 kg/21.18 kg). On a dry basis,the dried extrudate starting material for the pyrolysis is 40 wt. %carbon black and 60 wt. % binder. Assuming the mass of carbon black isunchanged by the pyrolysis, then on a dry basis the pyrolyzed extrudateshave a carbon black content of 69.6 wt. % and a carbonized bindercontent of 30.4 wt. %.

The pyrolyzed extrudates were analyzed for BET surface area and radialpiece crush strength, the results are shown in Table 19.

TABLE 19 Properties of Carbon Black Extrudate Pyrolyzed in aContinuously Operated Rotary Kiln Continuous Calculated N₂ BET RadialRotary Kiln Temperature Residence Specific Piece Pyrolyzed Set Point inTime in Surface Crush Extrudate Heating Zone Heating Zone Area StrengthSample Number (° C.) (minutes) (m²/g) (N/mm) 18.1 820 63 219 11.0 18.2820 44 208 10.5 18.3 800 44 202 10.8 18.4 780 44 188 11.3 18.5 760 44188 15.0 18.6 780 33 176 9.5 18.7 820 33 181 11.7

Example 19 Hydrodeoxygenation of Glucaric Acid Dilactone to Adipic Acid

Suitably concentrated aqueous solutions of rhodium nitrate and platinumnitrate were added together to carbon black powder (crushed from carbonblack pellets) by incipient wetness impregnation and agitated toimpregnate supports. The samples were dried in an oven at 60° C.overnight, and reduced at 350° C. under a forming gas (5% H₂ and 95% N₂)atmosphere for 4 hours with 2° C./min temperature ramp rate to producecatalysts with a composition of 1.0 wt. % Rh and 2.0 wt. % Pt. By usingother carbon blacks supports, Rh and Pt precursors, and adjusting amountof Rh and Pt in solution, different catalysts with various Rh and Ptloadings on a variety of particles from extrudates were prepared in asimilar manner.

These catalysts were tested for hydrodeoxygenation of glucaric aciddilactone using the following testing protocol. Catalyst (16 mg) wasweighed into a glass vial insert followed by addition of a solution (125μl) containing glucaric acid dilactone (0.80 M), HBr (0.80 M), and water(2.0 M). The glass vial insert was loaded into a reactor and the reactorwas closed. The atmosphere in the reactor was replaced with hydrogen andpressurized to 6307 kPa (900 psig) at room temperature. Reactor washeated to 120° C. and maintained at 120° C. for 1 hour while vials wereshaken. Reactor was then heated to 160° C. and maintained at 160° C. for2 hours while vials were shaken. After that, shaking was stopped andreactor was cooled to 40° C. Pressure in the reactor was slowlyreleased. The glass vial insert was removed from reactor andcentrifuged. The clear solution was hydrolyzed with NaOH, diluted withdeionized water, and analyzed by ion chromatography to determine theyield of adipic acid. The properties of the carbon black startingmaterials and results of the reaction screening are presented in Table20.

TABLE 20 Adipic Adipic Acid Surface Mean Pore Pore Acid Selec- AreaDiameter Volume Yield tivity Support (m²/g) (Å) (cm³/g) (%) (%) CabotMONARCH 25 277 0.1 75 83 120 Cabot MONARCH 30 176 0.1 81 91 280 TimcalENSACO 64 140 0.24 92 99 250P Cabot MONARCH 102 138 0.3 87 97 570 CabotMONARCH 181 121 0.38 89 99 700 Cabot VULCAN 224 161 0.43 86 99 XC72 SidRichardson SC159 234 182 0.81 75 86

Example 20 Testing of Rh/Pt Carbon Black Extrudate Catalysts in aFixed-Bed Reactor for Hydrodeoxygenation of Glucaric Acid to Adipic Acid

Cabot VULCAN XC72 carbon black particles used in this experiment were150 to 300 μm sized particles crushed and sieved from extrudate pelletsprepared from the method described in previous examples. Reactions wereconducted in a 6.4 mm (0.25-inch) OD by 38 cm long zirconium tube withco-current down-flow of gas and liquid. Catalyst beds were vibrationpacked with 200 to 300 μm sized glass beads at the top to approximately5 cm depth, followed by catalyst (28 cm bed depth containing 1.9 g, 0.90wt. % Rh+2.1 wt. % Pt on carbon black particles, 150 to 300 μm particlesize), then 200 to 300 μm sized glass beads at the bottom toapproximately 5 cm depth. Quartz wool plugs separated the catalyst bedfrom the glass beads.

The packed reactor tube was clamped in an aluminum block heater equippedwith PID controller. Gas (compressed hydrogen) and liquid flows wereregulated by mass flow controller and HPLC pump, respectively. Substratesolution contains 0.80M D-glucaric acid-1,4:6,3-dilactone, 0.40M HBr and2.0M water in acetic acid. A back pressure regulator controlled reactorpressure as indicated in Table 21. External temperature of top halfreactor and bottom half reactor was controlled at 110° C. and 160° C.respectively. The catalyst was tested for 350 hours on stream and showedstable performance. Table 21 describes the fixed bed reactor conditionsand resultant catalyst performance.

TABLE 21 Gas Glucaric acid Glucaric acid Reactor Liquid flowrate/dilactone Adipic Reactor block dilactone pressure/ flowrate/ mL min⁻¹conversion/ acid yield/ Test temperature/° C. concentration/M psi mLmin⁻¹ (STP) % % 1 110/160 0.80 1000 0.050 50 90 42

Example 21 Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol

Suitably concentrated aqueous solutions of Pt(NO₃)_(x) and H₄SiO₄*12WO₃or PtONO₃ and H₄SiO₄*12WO₃ were added to approximately 50 mg of ENSACO250G carbon and agitated to impregnate the supports. The samples weredried in an oven at 40° C. overnight under static air and then reducedat 350° C. under forming gas (5% H₂ and 95% N₂) atmosphere for 3 hours.The final catalysts had a metal content of approximately 4.09 wt. % Ptand 3.42 wt. % W.

These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenationusing the following catalyst testing protocol. Catalyst (approximately10 mg) was weighed into a glass vial insert followed by addition of anaqueous 1,2,6-hexanetriol solution (200 μl of 0.8 M). The glass vialinsert was loaded into a reactor and the reactor was closed. Theatmosphere in the reactor was replaced with hydrogen and pressurized to4721 kPa (670 psig) at room temperature. The reactor was heated to 160°C. and maintained at the respective temperature for 150 minutes whilevials were shaken. After 150 minutes, shaking was stopped and reactorwas cooled to 40° C. Pressure in the reactor was then slowly released.The glass vial insert was removed from the reactor and centrifuged. Thesolution was diluted with methanol and analyzed by gas chromatographywith flame ionization detection. The results are shown in Table 22.

TABLE 22 Surface Mean Pore Pore Area Diameter Volume Pt W YieldSelectivity Support (m²/g) (Å) (cm³/g) Precursor Precursor (%) (%)ENSACO 250G 64 140 0.24 Pt(NO₃)₂ H₄SiO₄*12WO₃ 27 64 ENSACO 250G 64 1400.24 PtONO₃ H₄SiO₄*12WO₃ 47 69

Example 22 Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol

A suitably concentrated aqueous solution of ammonium metatungstate,H₂₆N₆W₁₂O₄₀ was added to approximately 500 mg of ENSACO 250G andagitated to impregnate the carbon black support. The sample wasthermally treated at 600° C. under a nitrogen atmosphere for 3 hourswith 5° C./min temperature ramp rate. Suitably concentrated aqueoussolutions of Pt(NMe₄)₂(OH)₆ was added to 50 mg of the above sample andagitated to impregnate the carbon supports. The samples were dried in anoven at 40° C. overnight under static air and then reduced at 250° C.under forming gas (5% H₂ and 95% N₂) atmosphere for 3 hours with 5°C./min temperature ramp rate. The final catalysts had a metal content ofapproximately 4.5 wt. % Pt and 2 wt. % W.

These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenationusing the following catalyst testing protocol. Catalyst (approximately10 mg) was weighed into a glass vial insert followed by addition of anaqueous 1,2,6-hexanetriol solution (200 μl of 0.8 M). The glass vialinsert was loaded into a reactor and the reactor was closed. Theatmosphere in the reactor was replaced with hydrogen and pressurized to4721 kPa (670 psig) at room temperature. The reactor was heated to 160°C. and maintained at the respective temperature for 150 minutes whilevials were shaken. After 150 minutes, shaking was stopped and reactorwas cooled to 40° C. Pressure in the reactor was then slowly released.The glass vial insert was removed from the reactor and centrifuged. Theclear solution was diluted with methanol and analyzed by gaschromatography with flame ionization detection. The results are shown inTable 23.

TABLE 23 Surface Mean Pore Pore Area Diameter Volume Pt W YieldSelectivity Support (m²/g) (Å) (cm³/g) Precursor Precursor (%) (%)ENSACO 250G 64 140 0.24 Pt(NMe₄)₂(OH)₆ H₂₆N₆W₁₂O₄₀ 38 88

Example 23 Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol

Suitably concentrated aqueous solutions of ammonium metatungstate,H₂₆N₆W₁₂O₄₀ were added to approximately 500 mg of carbon black materialsand agitated to impregnate the carbon black supports. The samples werethermally treated at 600° C. under a nitrogen atmosphere for 3 hourswith 5° C./min temperature ramp rate. Suitably concentrated aqueoussolutions of Pt(NMe₄)₂(OH)₆ were added to approximately 50 mg of theabove samples and agitated to impregnate the carbon supports. Thesamples were dried in an oven at 60° C. under static air and thenreduced at 350° C. under forming gas (5% H₂ and 95% N₂) atmosphere for 3hours with 5° C./min temperature ramp rate. The final catalysts had ametal content of approximately 5.7 wt. % Pt and 1.8 wt. % W.

These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenationusing the following catalyst testing protocol. Catalyst (approximately10 mg) was weighed into a glass vial insert followed by addition of anaqueous 1,2,6-hexanetriol solution (200 μl of 0.8 M). The glass vialinsert was loaded into a reactor and the reactor was closed. Theatmosphere in the reactor was replaced with hydrogen and pressurized to4721 kPa (670 psig) at room temperature. The reactor was heated to 160°C. and maintained at the respective temperature for 150 minutes whilevials were shaken. After 150 minutes, shaking was stopped and reactorwas cooled to 40° C. Pressure in the reactor was then slowly released.The glass vial insert was removed from the reactor and centrifuged. Theclear solution was diluted with methanol and analyzed by gaschromatography with flame ionization detection. Results are shown inTable 24.

TABLE 24 Surface Mean Pore Pore Area Diameter Volume Pt W YieldSelectivity Support (m²/g) (Å) (cm³/g) Precursor Precursor (%) (%)ENSACO 250G 64 140 0.24 Pt(NMe₄)₂(OH)₆ H₂₆N₆W₁₂O₄₀ 52 71 Orion HIBLACK109 155 0.32 Pt(NMe₄)₂(OH)₆ H₂₆N₆W₁₂O₄₀ 28 68 40B2

Example 24 Small Scale Batch Reactor Experiments for Amination of1,6-Hexanediol to Produce 1,6-Hexamethylenediamine

Amination of 1,6-Hexanediol to produce1,6-Hexamethylenediamine—Analytical Details

Product composition was determined by HPLC analysis using a ThermoUltimate 3000 dual analytical chromatography system.Hexamethylenediamine (HMDA), hexamethyleneimine (HMI) and pentylaminewere eluted with a mobile phase consisting of H₂O/MeCN/TFA and detectedusing a charged aerosol detector (CAD). 1,6-Hexanediol (HDO) was elutedwith a mobile phase consisting of H₂O/MeCN/TFA and detected using arefractive index detector (RI). In certain examples an internalstandard, N-methyl-2-pyrrolidone (NMP), was used in the substrate feedto correct for variations in product effluent concentration due to NH₃off-gassing. NMP was eluted with a mobile phase consisting ofH₂O/MeCN/TFA and detected by UV at 210 nm. All products were quantifiedby comparison to calibration standards. Selectivity is reported as theyield of HMDA divided by the sum of HMDA and pentylamine.

Experiment 1

Preparation of Supported Ru Catalysts

A suitably concentrated aqueous solution of Ru(NO)(NO₃)₃ was added to a96 vial array of carbon supports containing 10 or 20 mg of support ineach vial. The volume of ruthenium solution was matched to equal thepore volume of the support. Each sample was agitated to impregnate thesupport. The samples were dried in an oven at 60° C. for 12 hours undera dry air purge. The catalysts were reduced under forming gas (5% H₂ and95% N₂) at 250° C. for 3 hours using a 2° C./min temperature ramp rate.The final catalysts were composed of 2 weight percent ruthenium.

Catalyst Screening Procedure

A substrate solution consisting of 0.7 M 1,6-hexanediol in concentratedaqueous NH₄OH was added to an array of catalysts prepared as describedabove. The vials were covered with a Teflon pinhole sheet, a siliconepinhole mat, and a steel gas diffusion plate. The reactor insert wasplaced in a pressure vessel and purged 2× with NH₃ gas. The pressurevessel was charged to 690 kPa (100 psi) with NH₃ gas and then to 4700kPa (680 psi) with N₂ at ambient temperature. The reactor was placed ona shaker and vortexed at 800 rpm at 160° C. After 3 hours, the reactorwas cooled to room temperature, vented, and purged with nitrogen priorto being unsealed. The samples were diluted with water, mixed, and thencentrifuged to separate catalyst particles. Aliquots were removed fromthe supernatant and diluted further with dilute aqueous trifluoroaceticacid for analysis by HPLC. Results are summarized below in Table 25.

TABLE 25 Surface Mean Pore Pore Catalyst HDO HMDA Pentylamine AreaDiameter Volume Amount Conversion Yield Yield Support (m²/g) (Å) (cm³/g)(mg) (%) (%) (%) Selectivity Asbury 5346R 80 145 0.28 10 79.8 16.5 0.099.8 Asbury 5346R 80 145 0.28 20 99.1 25.1 0.5 97.9 ENSACO 150G 47 1360.17 10 80.8 16.4 0.1 99.5 ENSACO 150G 47 136 0.17 20 95.5 24.5 0.7 97.4ENSACO 250G 64 140 0.24 10 78.6 16.3 0.0 100 ENSACO 250G 64 140 0.24 2094.4 26.0 0.5 98.2 ENSACO 260G 63 104 0.18 10 74.7 15.4 0.0 100 ENSACO260G 63 104 0.18 20 93.3 24.0 0.5 98.1 HP160 158 208 0.87 10 81.7 11.90.0 100 HP160 158 208 0.87 20 98.3 18.3 0.1 99.2 Orion HI-BLACK 193 1570.66 10 91.0 18.8 0.2 99.1 50L Orion HI-BLACK 193 157 0.66 20 100 21.70.7 96.8 50L Sid Richardson 234 182 0.81 10 90.3 14.7 0.0 100 SC159 SidRichardson 234 182 0.81 20 99.3 17.3 0.4 97.9 SC159 Sid Richardson 146222 0.87 10 93.2 19.5 0.1 99.5 SR155 Sid Richardson 146 222 0.87 20 10019.7 0.4 98.1 SR155

Experiment 2

Preparation of Supported Ru/Re Catalysts

Suitably concentrated aqueous solutions of Ru(NO)(NO₃)₃ containingvarying amounts of HReO₄ were added to 0.15 g of a support and agitatedto impregnate the support. The volume of metal solution was matched toequal the pore volume of the support. The samples were dried in an ovenat 60° C. for 3 hours under a dry air purge. Catalyst amounts from 10-20mg were weighed in to glass vials of a 96 vial array. The catalysts werereduced under forming gas (5% H₂ and 95% N₂) at 60° C. for 3 hours thenat 250° C. for 3 hours using a 2° C./min temperature ramp rate. Thefinal catalysts were composed of 4.04 weight percent rutheniumcontaining various rhenium loadings of 0, 0.4, 0.7, and 1.9 wt. %.

Catalyst Screening Procedure

A substrate solution consisting of 1.549M 1,6-hexanediol in concentratedaqueous NH₄OH was added to an array of catalysts prepared as describedabove. The vials were covered with a Teflon pinhole sheet, a siliconepinhole mat, and a steel gas diffusion plate. The reactor insert wasplaced in a pressure vessel and purged 2× with NH₃ gas. The pressurevessel was charged to 690 kPa (100 psi) with NH₃ gas and then to 4700kPa (680 psi) with N₂ at ambient temperature. The reactor was placed ona shaker and vortexed at 800 rpm at 160° C. After 3 hours, the reactorwas cooled to room temperature, vented, and purged with nitrogen priorto being unsealed. The samples were diluted with water, mixed, and thencentrifuged to separate catalyst particles. Aliquots were removed fromthe supernatant and diluted further with dilute aqueous trifluoroaceticacid for analysis by HPLC. Results are outline below in Table 26.

TABLE 26 Hexanediol to Hexamethylenediamine using Ru/Re/Carbon HP-160Catalysts HDO Pentyl- Catalyst Conver- HMDA amine HMDA/ Amount Ru Resion Yield Yield Pentyl- Entry (mg) (wt. %) (wt. %) (%) (%) (%) amine 120 4.04 0.0 95.8 20.2 1.4 14.5 2 20 4.04 0.4 98.7 23.2 1.3 18.1 3 204.04 0.7 99.4 23.4 1.0 23.3 4 20 4.04 1.9 97.4 20.3 0.4 51.8 5 10 4.040.0 79.5 14.4 0.6 26.1 6 10 4.04 0.4 90.4 20.1 0.7 27.9 7 10 4.04 0.792.6 20.7 0.6 35.8 8 10 4.04 1.9 78.3 11.5 0.0

Experiment 3

Preparation of Ni/Ru Catalysts Supported on ENSACO 250G

Suitably concentrated aqueous solutions containing Ni(NO₃)₂ and/orRu(NO)(NO₃)₃ were added by incipient wetness impregnation toapproximately 0.4 g of a carbon black support and agitated to impregnatethe support. The volume of metal solution was matched to equal the porevolume of the support. Each catalyst was thermally treated under N₂ in atube furnace at 60° C. for 12 hours then at 300° C. for 3 hours using a5° C./min temperature ramp rate.

Catalyst amounts from 15-25 mg were weighed in to glass vials of a 96vial array. The catalysts were reduced under forming gas (5% H₂ and 95%N₂) at 450° C. for 3 hours using a 2° C./min temperature ramp rate.Catalysts were passivated with 1% O₂ in N₂ at room temperature beforeremoving from the tube furnace.

Catalyst Screening Procedure A

A substrate solution consisting of 0.7M 1,6-hexanediol in concentratedaqueous NH₄OH was added to an array of catalysts prepared as describedabove. The vials were covered with a Teflon pinhole sheet, a siliconepinhole mat, and a steel gas diffusion plate. The reactor insert wasplaced in a pressure vessel and purged 2× with NH₃ gas. The pressurevessel was charged to 690 kPa (100 psi) with NH₃ gas and then to 4700kPa (680 psi) with N₂ at ambient temperature. The reactor was placed ona shaker and vortexed at 800 rpm at 160° C. After 3 hours, the reactorwas cooled to room temperature, vented, and purged with nitrogen priorto being unsealed. The samples were diluted with water, mixed, and thencentrifuged to separate catalyst particles. Aliquots were removed fromthe supernatant and diluted further with dilute aqueous trifluoroaceticacid for analysis by HPLC. Results are summarized below in Table 27.

TABLE 27 HDO Pentyl- Catalyst Conver- HMDA amine Amount Ni Ru sion YieldYield Selec- Entry (mg) (wt. %) (wt. %) (%) (%) (%) tivity 1 15 12 035.8 1.9 0.0 98.4 2 15 0 0.56 66.1 9.6 0.3 97.4 3 15 4 0.56 74.3 17.30.3 98.5 4 15 8 0.56 77.3 22.7 0.3 98.7 5 15 12 0.56 85.9 25.3 0.4 98.66 25 12 0 54.0 7.7 0.1 99.1 7 25 0 0.56 82.7 18.9 0.5 97.2 8 25 4 0.5689.1 29.0 0.8 97.5 9 25 8 0.56 92.8 31.4 0.7 97.7 10 25 12 0.56 94.730.1 0.7 97.6

Catalyst Screening Procedure B

Passivated catalysts were reactivated in water under H₂ at 180° C. for 3hours. Most of the water was removed from each catalyst leaving behindenough to act as a protective layer. The catalysts were then screened asdescribed above in Procedure A. Results are summarized below in Table28.

TABLE 28 HDO Pentyl- Catalyst Conver- HMDA amine Amount Ni Ru sion YieldYield Selec- Entry (mg) (wt. %) (wt. %) (%) (%) (%) tivity 1 15 12 049.2 7.2 0.00 100.0 2 15 0 0.56 67.0 11.2 0.06 99.5 3 15 4 0.56 73.718.2 0.07 99.7 4 15 8 0.56 86.8 25.5 0.38 98.5 5 15 12 0.56 86.0 23.80.33 98.7 6 25 12 0 73.3 16.0 0.00 100.0 7 25 0 0.56 83.8 18.3 0.84 95.68 25 4 0.56 93.5 28.1 1.22 95.9 9 25 8 0.56 94.0 27.8 1.07 96.3 10 25 120.56 96.1 27.3 1.15 96.0

Fixed Bed Experiments

Preparation of 2 wt. % Ru on Carbon ENSACO 250G

A carbon extrudate, prepared from carbon black ENSACO 250G and acarbohydrate binder, was crushed and sized to 150-300 um. A suitablyconcentrated aqueous solution of Ru(NO)(NO₃)₃ was added to 4.77 g of thecrushed extrudate and agitated to impregnate the support. The volume ofmetal solution was matched to equal the pore volume of the support. Thesamples were dried in an oven at 60° C. for 12 hours under a dry airpurge. The catalyst was reduced under forming gas (5% H₂ and 95% N₂) at250° C. for 3 hours using a 2° C./min temperature ramp rate. Thecatalyst was washed with water and again sized to 106-300 um to removeany fines that may have been generated during the metal impregnationstep.

Preparation of 10.5 wt. % Ni and 0.45 wt. % Ru on Carbon ENSACO 250G

A carbon extrudate, prepared from carbon black ENSACO 250G and acarbohydrate binder, was crushed and sized to 106-300 um. A suitablyconcentrated aqueous solution containing Ni(NO₃)₂.6H₂O and Ru(NO)(NO₃)₃was added to 10 g of the crushed extrudate and agitated to impregnatethe support. The volume of metal solution was matched to equal the porevolume of the support. The catalyst was dried in an oven at 60° C. for12 hours under a dry air purge then thermally treated under N₂ at 300°C. for 3 hours. The catalyst was reduced under forming gas (5% H₂ and95% N₂) at 450° C. for 3 hours using a 2° C./min temperature ramp rate.After cooling to room temperature the catalyst was passivated with 1% O₂in N₂ at room temperature before removing from the tube furnace. Thecatalyst was washed with water and again sized to 106-300 um to removeany fines that may have been generated during the metal impregnationstep.

2 wt. % Ru on Carbon Catalyst

The reaction was performed in a 6.4 mm (0.25-inch) OD by 570 mm long 316stainless steel tube with a 2 um 316 stainless steel frit at the bottomof the catalyst bed. The reactor was vibration packed with 1 g of SiCbeads (90-120 um) followed by 3 g of a 2% by weight ruthenium on carbonENSACO 250G catalyst (100-300 um) and finally 2.5 g of SiC beads at thetop. A 6.4 mm (0.25-inch) layer of glass wool was used between eachlayer. The packed reactor tube was vertically mounted in an aluminumblock heater equipped with PID controller. An HPLC pump was used todeliver liquid feed to the top of the reactor and a back pressureregulator was used to control reactor pressure. The reaction was run at160° C. Product effluent was collected periodically for analysis byHPLC. No decline in catalyst activity was observed after 1650 h.

Three different feed compositions were investigated at 160° C. with areactor pressure ranging from 800-1000 psi. In all casesN-methyl-2-pyrrolidone (NMP) was used as an internal standard.

Feed 1: 0.7M 1,6-hexanediol and 0.14M NMP in concentrated NH4OH.

Feed 2: 0.7M 1,6-hexanediol, 0.14M hexamethyleneimine, and 0.14M NMP inconcentrated NH4OH.

Feed 3: 1.54M 1,6-hexanediol, 0.308M hexamethyleneimine, and 0.308M NMPin concentrated NH₄OH.

The results are summarized below in Table 29.

10.5 wt. % Ni/0.45 wt. % Ru on Carbon Catalyst

The reaction was performed as described above for the Ru only catalyst.A total of 3 g of Ni/Ru catalyst was loaded into the reactor andreactivated at 180° C. under H₂ before introduction of the feedsolution. No decline in catalyst activity was observed after 650 h.Results are summarized below in Table 29.

TABLE 29 Feed Reactor HDO HMDA HMI Pentylamine Rate Pressure ConversionYield Yield Yield Catalyst Source (mL/min) (psi) (%) (%) (%) (%)Selectivity 2 wt. % Ru Feed 1 0.2 800 85 23 11 1.5 93.9 2 wt. % Ru Feed2 0.2 800 83 29 18 1.6 94.8 2 wt. % Ru Feed 3 0.15 1000 90 36 21 2.693.3 10.5 wt. % Feed 2 0.2 800 83 26 17 0.5 98.1 Ni/0.45% Ru

Example 25 Preparation of Carbon Black Extrudates using DifferentCellulosic Binder Components

Additional carbon black extrudates were prepared using the bindermixtures indicated in Table 30. The procedure for the preparation ofsamples 1-21 is as follows: 900 g of a binder solution containingglucose and polymeric binder (with the wt. % content listed in Table 30)was added to 400 g carbon black powder (Sid Richardson SC159) in aSimpson Laboratory Mix Muller, which was run for 2 hours to ensure goodmixing and kneading of the material. The material was then loaded into a2.54 cm (1-inch) Bonnot “BB Gun” Catalyst Extruder and extruded intospaghetti like strings with about a 1.6 mm diameter. These strings weredried under a dry air purge at 120° C. in an oven overnight and thenpyrolyzed in batch mode under a nitrogen atmosphere at 800° C. for 2hours with a temperature ramp of 30° C./minute. Sample 22 was preparedin accordance with this procedure with the exception that the bindersolution did not contain a polymeric binder. Sample 23 was also preparedin accordance with this procedure with the exception that the bindersolution did not contain glucose.

The polymeric binders listed in Table 30 are the following:

-   -   Dow CELLOSIZE EP-09 (EP-09), hydroxyethylcellulose;    -   Dow METHOCEL K100LV (K100LV), hydroxypropylmethylcellulose;    -   Dow METHOCEL A4C (A4C), methylcellulose;    -   Dow METHOCEL F50 (F50), hydroxypropylmethylcellulose;    -   Ashland NATROSOL 250GR (250GR), hydroxyethylcellulose;    -   Ashland NATROSOL 250JR (250JR), hydroxyethylcellulose;    -   Ashland NATROSOL 250LR (250LR), hydroxyethylcellulose; and    -   Dow CELLOSIZE QP-40 (QP-40), hydroxyethylcellulose.

TABLE 30 Radial Glucose Polymeric Vis- Piece N₂ BET Binder Binder cosityCrush Surface Sam- wt. % in Polymeric wt. % in (mPa · s, Strength Areaple Solution Binder Solution cPs) (N/mm) (m²/g) 1 47.2 EP-09 5.7 10 9.7180 2 48.1 EP-09 3.8 10 10.1 179 3 49.0 EP-09 2.0 10 18.7 175 4 47.2K100LV 5.7 100 10.6 172 5 48.1 K100LV 3.8 100 10.5 170 6 49.0 K100LV 2.0100 11.1 182 7 47.2 A4C 5.7 400 9.7 174 8 48.1 A4C 3.8 400 10.6 173 949.0 A4C 2.0 400 10.4 176 10 47.2 F50 5.7 50 9.2 174 11 48.1 F50 3.8 5010.7 177 12 49.0 F50 2.0 50 9.5 182 13 47.2 250GR 5.7 150 11.4 171 1448.1 250GR 3.8 150 11.1 163 15 49.0 250GR 2.0 150 10.2 175 16 47.2 250JR5.7 20 12.5 167 17 48.1 250JR 3.8 20 14.3 171 18 49.0 250JR 2.0 20 21.5171 19 47.2 250LR 5.7 12 14.8 170 20 48.1 250LR 3.8 12 10.1 170 21 49.0250LR 2.0 12 9.6 174 22 49.0 — — — 10.2 — 23 — QP-40 4.0 125 0.5 —

The viscosity reported in Table 30 is the approximate viscosity of a 2wt. % aqueous solution of the polymeric binder at 25° C. The extrudateswere analyzed for BET specific surface area and radial piece crushstrength. The results of these analyses are also provided in Table 30.Pore volume and mean pore diameter (BJH method) were also measured forthese pyrolyzed extrudates. The pore volume for these samples rangedfrom approximately 0.3 to 0.4 cm³/g. The mean pore diameter for thesesamples ranged from approximately 13 to 16 nanometers (130 to 160Angstroms).

The results in Table 30 show that radial piece crush strengths of mostof the samples are approximately 10-12 N/mm, with the exception of thelower viscosity hydroxyethylcellulose. The extrudates prepared witheither Dow CELLOSIZE EP-09 hydroxyethylcellulose and Ashland NATROSOL250JR hydroxyethylcellulose exhibit greater radial piece crush strengthas the weight percent of the polymeric binder decreases from 5.7 to 2.0wt. %.

Example 26 Evaluation of Belt Drying Conditions on Final Extrudate CrushStrength

An aqueous solution containing 101.5 g of Ashland NatrosolHydroxyethylcellulose 250 JR (viscosity 20 mPa·s (cP) at 2% in H₂O (25°C.)), and 2739 g glucose (ADM Corn Processing, Dextrose Monohydrate99.7DE with 91.2 wt. % Glucose content) in 2258 ml deionized water wasstirred in a heated drum at approximately 60° C. fitted with a mixer forapproximately 24 hours. This resultant solution was added over 8 minutesto 2281 g of Sid Richardson SC159 carbon black powder in a 45.7 cm (18inch) diameter Simpson mix-muller, the mixture was then mixed for afurther 20 minutes in the mix-muller. The material was then loaded intoa 5.7 cm (2.25-inch) diameter Bonnot Catalyst Extruder, fitted with 5dies with 26 cylindrical holes each 1.6 mm ( 1/16-inch) internaldiameter (JMP Industries, part number 0388P062), and no spacer, andextruded into spaghetti-like strings. The extrudate was then dried on acommercial scale continuous industrial belt dryer (200 cm (118 inches)wide, 1219 cm (480 inches) heated zone (3 independent heating zones,forced hot air, each 406 cm (160 inches) long), with a conveyor belt ofperforated steel sheets), equipped with three hot air temperature stagesset at 43° C., 110° C. and 110° C. The extrudate was dried on the beltdryer by passing the extrudate through the 3 temperature zones with anaggregate residence time of 75 minutes. Measurement of residual moistureon a moisture balance (using a temperature setting of 160° C. and a timeof 30 minutes for a 5 g sample) indicated the belt-dried extrudates had17.0% moisture remaining after the belt drying process. The extrudateswere further dried in an oven at 120° C. overnight, reducing theresidual moisture level to 11.7 wt. % as measured on a moisture balanceusing a temperature setting of 160° C. and a time of 30 minutes for a 5g sample. The extrudates were then pyrolyzed in batch mode using a 12.7cm (5-inch) quartz tube rotating at 4.0 rpm under a nitrogen atmosphereat 800° C. for 2 hours with a temperature ramp of 30° C./minute. Theresulting extrudate (1.4 mm diameter×3 mm to 7 mm length) wascharacterized with a radial piece crush strength in the range from about7 N/mm to about 10 N/mm, which is much lower than the crush strengthachievable with similar formulations prepared at laboratory scale andquickly dried in a laboratory oven at 130° C., as shown in Example 25,sample 18. The resulting extrudate was also characterized with a N₂ BETspecific surface area of 158 m²/g, a N₂ BJH adsorption specific porevolume of 0.37 cm³/g, and a N₂ BJH adsorption mean pore diameter of 14.9nm (149 Angstroms).

Example 27 Preparation of Carbon Black Extrudates using ImprovedContinuous Belt Drying and Batch Pyrolysis

An aqueous solution containing 101.5 g of Ashland NATROSOLHydroxyethylcellulose 250 JR (viscosity 20 mPa·s (cP) at 2% in H₂O (25°C.)), and 2739 g glucose (ADM Corn Processing, Dextrose Monohydrate 99.7DE with 91.2 wt. % Glucose content) in 2264 ml deionized water wasstirred at in a heated drum fitted with a mixer for 6.5 hours. Thisresultant solution was added over 3.5 minutes to 2272 g of SidRichardson SC159 carbon black powder in a 45.7 cm (18 inch) diameterSimpson mix-muller, the mixture was then mixed for a further 20 minutesin the mix-muller. The material was then loaded into a 5.7 cm(2.25-inch) diameter Bonnot Catalyst Extruder, fitted with 5 dies with26 cylindrical holes each 1.6 mm ( 1/16-inch) internal diameter (JMPIndustries, part number 0388P062), and no spacer, and extruded intospaghetti-like strings. Approximately 7.4 kg of the extrudate was driedon a commercial scale continuous industrial belt dryer 200 cm (118inches) wide, 1219 cm (480 inches) heated zone (3 independent heatingzones, forced hot air, each 406 cm (160 inches) long), with a conveyorbelt of perforated steel sheets), with the three hot air temperaturestages set at 110° C., 120° C., and 120° C. The extrudate was dried onthe belt dryer by passing a thin bed (approximately 1.27 cm (0.5 inches)in depth) of the extrudate through the three temperature zones with acumulative residence time of 75 minutes (25 minutes per zone) to produce5.2 kg of dried extrudate. Measurement of residual moisture on amoisture balance (using a temperature setting of 160° C. and a time of30 minutes for a 5 g sample) indicated the belt-dried extrudates had11.1 wt. % moisture remaining. The extrudates were further dried in anoven at 120° C. overnight, reducing the residual moisture level to 10.0wt. % as measured on a moisture balance using a temperature setting of160° C. and a time of 30 minutes for a 5 g sample. The carbon blackextrudates were pyrolyzed in batch mode under a nitrogen atmosphere(continuous nitrogen purge) at 800° C. for 2 hours with a temperatureramp of 30° C./minute. The resulting extrudate (1.4 mm diameter×3-7 mmlength) was characterized with a radial piece crush strength of 23 N/mm,which was significantly higher than was achieved in Example 26. Theresulting extrudate was also characterized with a N₂ BET specificsurface area of 193 m²/g, a N₂ BJH adsorption specific pore volume of0.39 cm³/g, and a N₂ BJH adsorption mean pore diameter of 14.9 nm (149Angstroms).

Example 28 Effect of Drying Conditions and Time between Drying andCalcining (Pyrolysis) on Final Extrudate Crush Strength

A set of experiments was designed to study the effect of dryingconditions, residual moisture level, and the time elapsed between dryingand pyrolysis (calcining) of the extrudates, on the strength of thefinal pyrolyzed (calcined) extrudates. The results are shown in Tables31 and 32 below.

Extrudates were dried in conventional laboratory oven with a dry airpurge, at the drying temperature and for the time shown in the tablebelow. Residual moisture content (wt. %) of the extrudates was measuredon moisture balance at 160° C. (5 g sample, dried to constant weightdefined as weight change less than 1 mg per 3 minutes, typically onehour per sample).

TABLE 31 Residual Moisture Content (wt. %) Dependence on Drying Time(hours) & Temperature (° C.) Drying Temperature Drying Time ResidualMoisture Content (° C.) (hours) (wt. %) 70 1 24.5 70 2 16.4 70 3 13.4 704 12.7 70 6 11.0 70 22 11.5 100 1 14.5 100 2 10.0 100 3 9.5 100 4 10.1100 6 9.4 100 22 9.7 130 1 8.6 130 2 8.9 130 3 9.0 130 4 8.0 130 6 8.0130 22 6.7

After storage in a water-tight container for the “Shelf Life” (elapsedtime between drying and pyrolysis) shown in Table 32 below, theextrudates were pyrolyzed (calcined) in a static furnace under nitrogenpurge, using a temperature ramp rate, from ambient temperature to 800°C., of 30° C. per minute, followed by holding at 800° C. for 2 hours,then cooling to ambient temperature. The radial piece crush strength(N/mm) was then measured for each sample of pyrolyzed (calcined)extrudates. The results are shown in Table 32 below.

TABLE 32 Effect of Residual Moisture and Elapsed Time Between Drying andPyrolysis on the Final Extrudate Crush Strength Shelf Life Shelf LifeRadial Drying Mois- (time between (time between Piece Tempera- Dryingture drying and drying and Crush ture Time Content pyrolysis, pyrolysis,Strength (° C.) (hours) (wt. %) hours) days) (N/mm) 70 2 16.4 3 0.1 13.670 2 16.4 27 1.1 13.4 70 2 16.4 99 4.1 5.7 70 2 16.4 388 16.2 3.0 70 313.4 20 0.8 12.0 70 3 13.4 50 2.1 9.8 70 3 13.4 406 16.9 3.8 70 4 12.719 0.8 14.3 70 4 12.7 49 2.0 11.4 70 4 12.7 170 7.1 9.5 70 4 12.7 40516.9 9.6 70 6 11.0 41 1.7 10.7 70 6 11.0 411 17.1 12.6 100 1 14.5 4 0.29.2 100 1 14.5 28 1.2 9.9 100 1 14.5 100 4.2 9.2 100 1 14.5 389 16.2 3.8100 2 10.0 3 0.1 12.1 100 2 10.0 27 1.1 10.5 100 2 10.0 99 4.1 9.2 100 210.0 388 16.2 12.6 100 3 9.5 20 0.8 8.5 100 3 9.5 50 2.1 10.0 100 3 9.5171 7.1 10.1 100 3 9.5 406 16.9 12.1 100 6 9.4 41 1.7 12.2 100 6 9.4 41117.1 9.8

As the table shows, when the residual moisture content (wt. %) of thedried extrudates was higher than 11 wt. %, there was a decline in theradial piece crush strength (N/mm) of the pyrolyzed (calcined)extrudates with increasing “Shelf Life” (elapsed time between drying andpyrolysis). The reduction in crush strength of the pyrolyzed (calcined)extrudates was especially evident for samples that had residual moisturecontent (wt. %) of the dried extrudates higher than 13 wt. %. When theresidual moisture content (wt. %) of the dried extrudates was lower than11 wt. %, the crush strength of the pyrolyzed (calcined) extrudatesremained high. Surprisingly, the residual moisture content of the driedextrudates had an effect on the crush strength of the pyrolyzed(calcined) extrudates. When the residual moisture content was aboveabout 11 wt. %, then the crush strength of the pyrolyzed (calcined)extrudates was negatively affected with increasing “Shelf Life” (elapsedtime between drying and pyrolysis). However, when the residual moisturecontent was at or below about 11 wt. %, then the crush strength was notcompromised even when the dried extrudates were stored for an extendedperiod of time (2 weeks) before pyrolysis (carbonization).

Example 29 Evaluation of Continuous Belt Drying Conditions andContinuous Rotary Kiln Residence Time and Conditions on Final PyrolyzedExtrudate Crush Strength

An aqueous solution containing 1.9 kg of Ashland NatrosolHydroxyethylcellulose 250 JR (viscosity 20 mPa·s (cP) at 2% in H₂O (25°C.)), and 49.9 kg of glucose (ADM Corn Processing, Dextrose Monohydrate99.7DE with 91.2 wt. % Glucose content) in 41.4 kg deionized water wasstirred in a 35 gallon drum fitted with a mixer and an immersion heaterat about 70° C. overnight. 59.5 kg of the resulting solution was addedover 10 minutes to 27.21 kg of Sid Richardson SC159 carbon black powderin a 91.4 cm (36 inch) diameter Simpson mix-muller, the mixture was thenmixed at high speed for a further 30 minutes in the mix-muller.

The material was then loaded into a 10.16 cm (4 inch) diameter BonnotCatalyst Extruder fitted with 6 dies, each with 26 cylindrical holes of1.6 mm ( 1/16-inch) internal diameter (JMP Industries, part number0388P062), and extruded into spaghetti-like strings. The extrudate wasthen dried on a commercial scale continuous industrial belt dryer, whichwas 104.4 cm (41 inches) wide, 330.2 cm (130 inches) heated zone (forcedhot air from single main burner split into 3 heating zones, eachcontrolled with valves above the belt to control flow of hot air andvalves below the bed to control the exhaust and thus cold air flow, withfirst and second zones each 114.34 cm (45 inches) long, the third zone101.6 cm (40 inches) long, with a conveyor belt of steel mesh.

The material was passed through the belt dryer with the threetemperature zones set such that the thermocouples in the first, secondand third heater zones above the belt were reading 130° C., 170° C. and225° C., and thermocouples in the first, second and third heater zonesbelow the belt were reading 101° C., 114° C. and 49° C. Thermocoupleswere inserted into the bed of extrudates on the belt periodically duringthe drying process, with typical readings of 95° C., 130° C. and 60° C.in the first, second and third heater zones respectively. The belt wasrun relatively slowly to achieve a total residence time in the heatedzones of about 60 minutes. Measurement of residual moisture on amoisture balance (using a temperature setting of 160° C. and a time of15 minutes) indicated the belt-dried extrudates had 25 wt. % moistureremaining.

The material was passed through the belt dryer for a second time withhigher hot air flow rate and with the three temperature zones set suchthat the thermocouples in the first, second and third heater zones abovethe belt were reading 132° C., 138° C. and 120° C., and thermocouples inthe first, second and third heater zones below the belt were reading 71°C., 88° C. and 32° C. A high air flow rate was used. Thermocouples wereinserted into the bed of extrudates on the belt periodically during thedrying process, with typical readings of 100° C., 125° C. and 100° C. inthe first, second and third heater zones respectively. The belt was runrelatively quickly to achieve a total residence time in the heated zonesof about 20 minutes. Measurement of residual moisture on a moisturebalance (using 5 g of sample, a temperature setting of 160° C. and atime of 30 minutes) indicated the belt-dried extrudates had 9.0 wt. %moisture remaining, which was below the threshold level of 11 wt. % andso met the drying target.

Example 30 Preparation of Carbon Black Extrudates using ContinuousPyrolysis in a Multi-Temperature Zone Rotary Kiln

Dried extrudate material from the large scale preparation described inExample 29 was charged to a vibratory feeder and fed under a nitrogenpurge into and through a multi-temperature zone rotary kiln. The threeheated zones of the rotary kiln were each 50.8 cm (20 inches) in length,for a total heated length of 152.4 cm (60 inches). The rotary kiln Zone1/Zone 2/Zone 3 temperatures were set to 450° C./600° C./800° C.respectively. The speed of the screw feeder was adjusted to between 5 kgof extrudate per hour. The angle of inclination and rotation rate of therotary kiln were adjusted to maintain a desired residence time in the152.4 cm (60 inch) heated zone of the kiln. The target average residencetime was 60 minutes, while the actual average residence time calculatedafter the run was 50 minutes. A nitrogen purge was also applied to boththe entrance and exit of the furnace, and to the product collectionvessel. The pyrolyzed extrudate was collected in a collection vesselunder a nitrogen purge and volatile products that result from thepyrolysis were sent to a cooled collection vessel (for condensables) fordownstream waste processing, with off-gases going to an afterburner.

Table 33 presents the process conditions for the multi-temperature zonerotary kiln. The surface area, pore volume and mean pore diameter, andthe crush strength of the resulting pyrolyzed extrudates are shown inTable 34. The crush strength of 15.4 N/mm, was a significant improvementcompared with previous Examples that employed continuous belt drying.

TABLE 33 Total Steady Kiln Temperature Residence State Volu- (° C.) Timein the 3 Feed Sample metric Zone Zone Zone Heated Zones Rate Time FeederTest 1 2 3 (minutes) (kg/hr) (hours) Type 1 450 600 800 50.3 5 2 Vibra-tory

TABLE 34 Steady State N₂ BJH Steady State % fines Product after N₂ BJHAdsorption Product before (sieved sieving to N₂ BET Adsorption Mean PoreRadial Piece sieving on 1 mm remove fines Surface area Pore volumediameter Crush Strength Test (g) screen) (g) (m²/g) (cm³/g) (Å) (N/mm) 13,972 1.8 3.90 176 0.30 127 15.4

Example 31 Evaluation of Extrusion Recipe Moisture Content, ContinuousBelt Drying Conditions and Continuous Rotary Kiln Residence Time andconditions on Final Pyrolyzed Extrudate Crush Strength

An aqueous solution containing 3.1 kg of Ashland NatrosolHydroxyethylcellulose 250 JR (viscosity 20 mPa·s (cP) at 2% in H₂O (25°C.)), and 82.9 kg of glucose (ADM Corn Processing, Dextrose Monohydrate99.7DE with 91.2 wt. % Glucose content) in 36.1 kg deionized water wasstirred in a 35 gallon drum fitted with a mixer and an immersion heaterat about 70° C. overnight. 46.9 kg of the resulting solution was addedover 10 minutes to 27.21 kg of Sid Richardson SC159 carbon black powderin a 91.4 cm (36 inch) diameter Simpson mix-muller, the mixture was thenmixed at high speed for a further 30 minutes in the mix-muller.

The material was then loaded into a 10.16 cm (4 inch) diameter BonnotCatalyst Extruder fitted with 18 dies, each with 26 cylindrical holes of1.6 mm ( 1/16-inch) internal diameter (JMP Industries, part number0388P062), and extruded into spaghetti-like strings. The extrudate wasthen dried on a commercial scale continuous industrial belt dryer, whichwas 104.14 cm (41 inches) wide, 330.2 cm (130 inches) heated zone(forced hot air from single main burner split into 3 heating zones, eachcontrolled with valves above the belt to control flow of hot air andvalves below the bed to control the exhaust and thus cold air flow, withfirst and second zones each 114.3 cm (45 inches) long, the third zone101.6 cm (40 inches) long, with a conveyor belt of steel mesh.

The material was passed through the belt dryer twice, with high hot airflow rate and with the three temperature zones set such that thethermocouples in the first, second and third heater zones above the beltwere reading 135° C., 177° C. and 149° C., and thermocouples in thefirst, second and third heater zones below the belt were reading 102°C., 113° C. and 46° C. Thermocouples were inserted into the bed ofextrudates on the belt periodically during the drying process, withtypical readings of 130° C., 175° C. and 120° C. in the first, secondand third heater zones respectively. The belt was run relatively quicklyto achieve a total residence time in the heated zones of about 15minutes per pass, for a total drying residence time of about 30 minutesfor the 2 passes. Measurement of residual moisture on a moisture balance(using 5 g of sample, a temperature setting of 160° C. and a time of 30minutes) indicated the belt-dried extrudates had 9.8 wt. % moistureremaining, which was below the threshold level of 11 wt. % and so metthe drying target.

A second batch extrudates was prepared by combining in the mix muller bycombining another 46.9 kg of the dextrose/hydroxyethylcellulose/watersolution with another 27.21 kg of Sid Richardson SC159 carbon blackpowder in the 91.4 cm (36 inch) diameter Simpson mix-muller, andrepeating the mix-mulling, extrusion and belt drying process (twopasses, each 15 minutes) described above. Measurement of residualmoisture on a moisture balance (using 5 g of sample, a temperaturesetting of 160° C. and a time of 30 minutes) indicated the belt-driedextrudates had 8.7 wt. % moisture remaining, which again was below thethreshold level of 11 wt. % and so met the drying target.

The whole preparation of the dextrose/hydroxyethylcellulose/watersolution, the mix-mulling and extrusion, and the 2-pass belt dryingprocess, as described above, was repeated again to produce two morebatches of dried extrudates. Measurement of residual moisture on amoisture balance using the same procedure indicated the third and fourthbatches of belt-dried extrudates both had 8.8 wt. % moisture remaining,which again was below the threshold level of 11 wt. % and so met thedrying target.

The total combined weight of the 4 batches of dried extrudates was 229kg. The average moisture content was 9.0%.

Example 32 Preparation of Carbon Black Extrudates using ContinuousPyrolysis in a Multi-Temperature Zone Rotary Kiln

A total of 213.5 kg of dried extrudate material from the four largescale preparations described in Example 31 was charged to an AcrisonModel 105X-D volumetric feeder fitted with an open helical Augermetering screw feeder, and fed under a nitrogen purge into and through amulti-temperature zone rotary kiln. The three heated zones of the rotarykiln were each 50.8 cm (20 inches) in length, for a total heated lengthof 152.4 cm (60 inches). The rotary kiln Zone 1/Zone 2/Zone 3temperatures were set to 450° C./600° C./800° C. respectively. The speedof the screw feeder was adjusted to between 5 kg of extrudate per hour.The angle of inclination and rotation rate of the rotary kiln wereadjusted to maintain a desired residence time in the 152.4 cm (60 inch)heated zone of the kiln. The target average residence time was 60minutes, while the actual average residence time calculated after theruns was between 53 and 73 minutes, as adjustments were made to target60 minutes residence time. A nitrogen purge was also applied to both theentrance and exit of the furnace, and to the product collection vessel.The pyrolyzed extrudate was collected in a collection vessel under anitrogen purge and volatile products that result from the pyrolysis weresent to a cooled collection vessel (for condensables) for downstreamwaste processing, with off-gases going to an afterburner.

Of the 213.5 kg of dried extrudate material charged to the feeder, 7.6kg remained in the feeder or feed section of the kiln, thus a total of205.9 kg of dried extrudate was passed though the kiln. A total of 106.5kg of pyrolyzed product was collected, for a simple “as is” mass-basedyield of 51.7%.

Measurement of residual moisture on a moisture balance (using atemperature setting of 160° C. and a time of 30 minutes for a 5g sample)indicated the continuous-pyrolyzed extrudates had 1.0 wt. % moisture,giving a dry-basis yield of 105.4 kg. Since the dried extrudate startingmaterial for the pyrolysis had a moisture level of 17.7 wt. %, the 205.9kg of feed represents 187.4 kg on a dry basis, and thus the yield of thepyrolysis on a dry basis is 56.2% (105.4 kg/187.4 kg).

On a dry basis, the dried extrudate starting material for the pyrolysisis 46.9 wt. % carbon black and 53.1 wt. % binder (taking into accountthe measure moisture content of the extrusion starting materials(measured on a moisture balance using a temperature setting of 160° C.and a time of 30 minutes for a 5 g sample), which were 2.8% for thecarbon black, 9.7% for the Dextrose Monohydrate, and 4.7% for theHydroxyethyl cellulose. Thus, assuming the mass of carbon black isunchanged by the pyrolysis, then on a dry basis the pyrolyzed extrudateshave a carbon black content of 83.4 wt. % and a carbonized bindercontent of 16.6 wt. %.

Table 35 presents the process conditions for the multi-temperature zonerotary kiln. The surface area, pore volume and mean pore diameter, andthe crush strength of the resulting pyrolyzed extrudates are shown inTable 36. The crush strengths for the four batches ranged from 14.0 N/mmto 18.4 N/mm, with an average of 15.6 N/mm. This demonstrated that thefaster belt drying method used for these examples was as good as theslower methods used in the previous example, and again gave asignificant improvement in final (pyrolyzed) extrudate crush strengthcompared with the Examples that employed continuous belt drying.

TABLE 35 Total Steady Kiln Temperature Residence State Volu- (° C.) Timein the 3 Feed Sample metric Zone Zone Zone Heated Zones Rate Time FeederBatch 1 2 3 (minutes) (kg/hr) (hours) Type 1 450 600 800 72.6 5 7 OpenHelical Auger 2 450 600 800 53.4 5 9 Open Helical Auger 3 450 600 80060.0 5 9 Open Helical Auger 4 450 600 800 64.3 5 7 Open Helical Auger

TABLE 36 Steady State N₂ BJH Steady State % fines Product after N₂ BJHAdsorption Product before (sieved sieving to N₂ BET Adsorption Mean PoreRadial Piece sieving on 1 mm remove fines Surface area Pore volumeDiameter Crush Strength Batch (g) screen) (g) (m²/g) (cm³/g) (Å) (N/mm)1 17,270 5.6 16.28 175 0.33 148 14.0 2 24,285 7.3 22.49 174 0.34 15815.9 3 23,528 7.6 21.73 173 0.34 152 14.0 4 17,390 7.3 16.13 178 0.37161 18.4 Mean 175 0.35 155 15.6 Value

When introducing elements of the present invention or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

In view of the above, it will be seen that the several objects of theinvention are achieved and other advantageous results attained.

As various changes could be made in the above compositions, methods, andprocesses without departing from the scope of the invention, it isintended that all matter contained in the above description and shown inthe accompanying drawings] shall be interpreted as illustrative and notin a limiting sense.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

1. A process for preparing a shaped porous carbon product, the processcomprising: mixing a carbonaceous material and an organic binder to forma carbon-binder mixture, wherein the binder comprises: (i) a saccharideselected from the group consisting of a monosaccharide, a disaccharide,an oligosaccharide, a derivative thereof, and any combination thereofand/or (ii) a water soluble polymer; forming the carbon-binder mixtureto produce a shaped carbon composite; and heating the shaped carboncomposite in a heating zone to carbonize the binder thereby producingthe shaped porous carbon product.
 2. The process of claim 1 wherein theheating zone comprises at least two heating stages that are eachmaintained at an approximately constant temperature and the temperatureof each stage differs by at least about 50° C., with the temperatureincreasing from one stage to the next.
 3. The process of claim 2 whereinthe temperature of each stage differs by from about 50° C. to about 500°C.,
 4. The process of claim 1 wherein the heating zone comprises atleast six heating stages that are each maintained at an approximatelyconstant temperature and the temperature of each stage independentlydiffers by at least about 50° C., from the preceding stage. 5-9.(canceled)
 10. The process of claim 2 wherein the heating zone comprisesa multi-stage continuous rotary kiln.
 11. The process of claim 1 whereinthe carbon-binder mixture further comprises a solvent. 12-15. (canceled)16. The process of claim 11 wherein the process further comprises dryingthe shaped carbon composite to remove at least a portion of the solventcontained therein. 17-18. (canceled)
 19. The process of claim 16 whereinthe water content of the shaped carbon composite after drying is in therange of from about 2 wt. % to about 15 wt. 20-21. (canceled)
 22. Theprocess of claim 16 wherein the heating zone further comprises one ormore stages for drying the shaped carbon composite.
 23. The process ofclaim 16 wherein the heating zone comprises a belt conveyor furnace.24-26. (canceled)
 27. The process of claim 1 wherein the bindercomprises: (i) a saccharide selected from the group consisting of amonosaccharide, a disaccharide, an oligosaccharide, a derivativethereof, and any combination thereof and (ii) a water soluble polymer,wherein a 2 wt. % aqueous solution of the water soluble polymer has aviscosity of no greater than about 500 mPa·s at 25° C. and/or the watersoluble polymer has a number average molecular weight (M_(n)) that is nogreater than about 50,000 g/mol. 28-33. (canceled)
 34. The process ofclaim 1 wherein the shaped carbon composite is heated to a finaltemperature in the range of from about 400° C. to about 1,000° C. in theheating zone. 35-37. (canceled)
 38. The process of claim 1 wherein theshaped carbon composite is formed by extruding the carbon-bindermixture.
 39. (canceled)
 40. The process of claim 1 wherein the weightratio of binder to carbonaceous material in the carbon-binder mixture isfrom about 1:4 to about 3:1. 41-75. (canceled)
 76. The process of claim1 wherein the shaped porous carbon product has a radial piece crushstrength greater than about 4.4 N/mm (1 lb/mm).
 77. (canceled)
 78. Theprocess of claim 1 wherein the shaped porous carbon product has amechanical piece crush strength greater than about 22 N (5 lbs). 79-86.(canceled)
 87. The process of claim 1 wherein the carbonaceous materialis selected from the group consisting of activated carbon, carbon black,graphite, and combinations thereof.
 88. The process of claim 1 whereinthe carbonaceous material comprises carbon black. 89-90. (canceled) 91.The process of claim 88 wherein the carbon black has a BET specificsurface area from about 5 m²/g to about 500 m²/g.
 92. A shaped porouscarbon product comprising: carbon black and a carbonized bindercomprising a carbonization product of an organic binder. wherein theshaped porous carbon product has a BET specific surface area from about5 m²/g to about 500 m²/g, a mean pore diameter greater than about 10 nm,a specific pore volume greater than about 0.1 cm³/g, a radial piececrush strength greater than about 4.4 N/mm (1 lb/mm), and a carbon blackcontent of at least about 35 wt. %, and wherein the shaped porous carbonproduct has improved wettability as compared to shaped porous carbonproduct control
 1. 93. A highly wettable shaped porous carbon productcomprising a carbon agglomerate comprising a carbonaceous materialwherein the shaped porous carbon product has a diameter of at leastabout 50 μm, a BET specific surface area from about 5 m²/g to about 500m²/g, a mean pore diameter greater than about 10 nm, a specific porevolume greater than about 0.1 cm³/g, and a radial piece crush strengthgreater than about 4.4 N/mm (1 lb/mm), and wherein the shaped porouscarbon product has improved wettability as compared to shaped porouscarbon product control
 1. 94-126. (canceled)
 127. A catalyst compositioncomprising the shaped porous carbon product of claim 92 as a catalystsupport and a catalytically active component or precursor thereof.128-134. (canceled)
 135. A catalyst composition comprising the shapedporous carbon product of claim 93 as a catalyst support and acatalytically active component or precursor thereof.